Organic electroluminescent materials and devices

ABSTRACT

Novel heteroleptic iridium carbene complexes are provided. The complexes have lower-than expected sublimation temperatures, which is beneficial for the processing of these materials in solid state applications. Selective substitution of the ligands provides for phosphorescent compounds that are suitable for use in a variety of OLED devices. The carbene complexes can also be used as materials in a hole blocking layer and/or an electron transport layer to improve device performance.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No. 14/113,533, filed Jan. 13, 2014, which is a § 371 National Phase of International Application No. PCT/US2012/040993, filed Jun. 6, 2012, which claims priority to U.S. Application Ser. No. 61/494,667, filed Jun. 8, 2011, the entireties of which are incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

The present invention relates to novel heteroleptic iridium carbene complexes and organic light emitting devices (OLEDs) with novel device architectures. In particular, these iridium complexes are phosphorescent and are useful as emitters in OLED devices.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.

One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

SUMMARY OF THE INVENTION

In one aspect, a compound comprising a heteroleptic iridium complex having the formula:

is provided.

R₂, R_(x), R_(a), and R_(b), represent mono, di, tri, tetra substitutions or no substitution, and R₁ is an alkyl or cycloalkyl with a molecular weight higher than 15.5 g/mol. X is selected from the group consisting of CRR′, SiRR′, C═O, N—R, B—R, O, S, SO, SO₂, and Se. R, R′, R₂, R_(x), R_(a), R_(b), and R_(c) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and any two adjacent substituents are optionally joined to form a ring, which may be further substituted. n is 1 or 2.

In one aspect, n is 2. In one aspect, n is 1. In one aspect, X is O. In one, aspect X is S. In one aspect, R₁ contains at least 2 carbons. In one aspect, R₁ contains at least 3 carbons.

In one aspect, R₁ is independently selected from the group consisting of: ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, and cyclohexyl, wherein each group is optionally partially or fully deuterated.

In one aspect, R₁ contains at least one deuterium.

In one aspect, R_(c) comprises at least one chemical group selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, and fluorine.

In one aspect, the compound has the formula:

In one aspect, the compound has the formula:

wherein R₃, R₆ and R₇ represent mono, di, tri, tetra substitutions or no substitution, wherein R₃, R₄, R₅, R₆ and R₇ are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein two adjacent substituents of R₃, R₆ and R₇ are optionally joined to form a ring and may be further substituted; and wherein at least one of R₄ and R₅ is not hydrogen or deuterium.

In one aspect, the compound has the formula:

In one aspect, both R₄ and R₅ are not hydrogen or deuterium. In one aspect, both R₄ and R₅ are alkyl or cycloalkyl. In one aspect, both R₄ and R₅ are aryl or heteroaryl.

In one aspect, the compound has the formula:

wherein Y₁ to Y₄ is CR₈ or N, and wherein each R₈ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein any two adjacent substituents of R₈ are optionally joined to form a ring and may be further substituted.

In one aspect, the compound has the formula:

wherein R₃, R₆ and R₇ represent mono, di, tri, tetra substitutions or no substitution, wherein R₃, R₄, R₅, R₆ and R₇ are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein two adjacent substituents of R₃, R₆ and R₇ are optionally joined to form a ring and may be further substituted; and wherein at least one of R₄ and R₅ is not hydrogen or deuterium.

In one aspect, the compound has the formula:

In one aspect, the compound has the formula:

wherein R₁₂, R₁₃ and R₁₄ represent mono, di, tri, tetra substitutions or no substitution, wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, wherein two adjacent substituents of R₁₂, R₁₃ and R₁₄ are optionally joined to form a ring and may be further substituted; and wherein at least one of R₁₀ and R₁₁ is not hydrogen or deuterium.

In one aspect, the compound has the formula:

In one aspect, both R₁₀ and R₁₁ are not hydrogen or deuterium. In one aspect, both R₁₀ and R₁₁ are alkyl or cycloalkyl. In one aspect, both R₁₀ and R₁₁ are aryl or heteroaryl.

In one aspect, the compound has the formula:

wherein Y₁ to Y₄ is CR₈ or N, and wherein each R₈ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein any two adjacent substituents of R₈ are optionally joined to form a ring and may be further substituted.

In one aspect, the compound has the formula:

In one aspect, the compound is selected from the group consisting of:

wherein X is O or S and Z is O or S. R₁ is selected from the group consisting of methyl-d3, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, and cyclohexyl, wherein each group is optionally partially or fully deuterated.

R₄, R₅, R₁₀, R₁₁, R₂₁ and R₂₂ are each independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and combinations thereof, and wherein each group is optionally partially or fully deuterated.

In one aspect, the compound has the formula:

wherein R₁, R₄, and R₅ are alkyl.

In one aspect, R₁, R₄, and R₅ are iso-propyl.

In one aspect, R₁ is methyl-d3.

In one aspect a first device is provided. The first device comprises an organic light emitting device, further comprising an anode, a cathode, and an organic layer, disposed between the anode and the cathode, comprising a compound having the formula:

is provided.

R₂, R_(x), R_(a), and R_(b), represent mono, di, tri, tetra substitutions or no substitution, and R₁ is an alkyl or cycloalkyl with a molecular weight higher than 15.5 g/mol. X is selected from the group consisting of CRR′, SiRR′, C═O, N—R, B—R, O, S, SO, SO₂, and Se. R, R′, R₂, R_(x), R_(a), R_(b), and R_(c) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and any two adjacent substituents are optionally joined to form a ring, which may be further substituted. n is 1 or 2.

In one aspect, the organic layer is an emissive layer and the compound is an emissive dopant.

In one aspect, the organic layer further comprises a host.

In one aspect, the host comprises at least one of the chemical groups selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

In one aspect, the host is a metal complex.

In one aspect, the host is a metal carbene complex.

In one aspect, the metal carbene complex is selected from the group consisting of:

In one aspect, the device further comprises a second organic layer that is a non-emissive layer between anode and the emissive layer; and wherein the material in the second organic layer is a metal carbene complex.

In one aspect, the device further comprises a third organic layer that is a non-emissive layer between cathode and the emissive layer; and wherein the material in the third organic layer is a metal carbene complex.

In one aspect, the device further comprises a second organic layer that is a non-emissive layer and the compound of Formula I is a material in the second organic layer.

In one aspect, the second organic layer is a hole transporting layer and the compound of Formula I is a transporting material in the second organic layer.

In one aspect, the second organic layer is a blocking layer and the compound having Formula I is a blocking material in the second organic layer.

In one aspect, the first device is an organic light-emitting device.

In one aspect, the first device is a consumer product.

In one aspect, the first device comprises a lighting panel.

In one aspect, a first device is provided. The first device comprising an organic light emitting device, further comprising an anode, a cathode, a first layer disposed between the anode and the cathode, and a second layer disposed between the first layer and the cathode, wherein the first layer is an emissive layer comprising an emissive dopant and a host and the second layer is a non-emissive layer comprising a first metal carbene complex.

In one aspect, the host is a second metal carbene complex.

In one aspect, the host is an organic compound.

In one aspect, the device further comprises a third layer disposed between anode and the first layer; and wherein the third layer that is a non-emissive layer comprises a third metal carbene complex.

In one aspect, the second layer is a hole blocking layer.

In one aspect, the second layer is an exciton blocking layer.

In one aspect, the second layer is an electron transporting layer.

In one aspect, the third layer is an electron blocking layer.

In one aspect, the third layer is an exciton blocking layer.

In one aspect, the third layer is a hole transporting layer.

In one aspect, the first layer further comprises a non-emissive dopant, and wherein the non-emissive dopant is a fourth metal-carbene complex.

In one aspect, the emissive dopant is a fifth metal-carbene complex.

In one aspect, the second metal carbene complex is the first metal carbene complex.

In one aspect, the materials deposited between the anode and the cathode comprises essentially metal carbene complexes.

In one aspect, the first metal carbene complex has the formula:

wherein M is a metal having an atomic number greater than 40. A₁, A₂ are each independently selected from the group consisting of C or N. A and B are each independently a 5 or 6-membered carbocyclic or heterocyclic ring. R_(A) and R_(B) represent mono, di, tri, or tetra substitutions or no substitution, and X is selected from the group consisting of NR_(C), PR_(C), O, and S. Each of R_(A), R_(B), and R_(C) are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein any two adjacent substituents are optionally joined together to form a ring, which may be further substituted. The ligand L is another ligand coordinated to the metal M, wherein m is a value from 1 to the maximum number of ligands that may be attached to the metal, and wherein m+n is the maximum number of ligands that may be attached to metal M.

In one aspect, the metal is Ir or Pt.

In one aspect, X is NR_(C).

In one aspect, R_(B) is a fused heterocyclic ring; wherein the heteroatom in the fused heterocyclic ring is N; and wherein the fused heterocyclic ring is optionally further substituted.

In one aspect, R_(A) is an electron withdrawing group with Hammett constant larger than 0.

In one aspect, the first metal carbene complex is selected from the group consisting of:

In one aspect, the first device is an organic light-emitting device.

In one aspect, the first device is a consumer product.

In one aspect, the first device comprises a lighting panel.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

FIG. 3 shows a compound of Formula I.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F.sub.4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. patent application Ser. No. 10/233,470, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.).

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.

In one embodiment, a compound comprising a heteroleptic iridium complex having the formula:

is provided.

R₂, R_(x), R_(a), and R_(b), represent mono, di, tri, tetra substitutions or no substitution, and R₁ is an alkyl or cycloalkyl with a molecular weight higher than 15.5 g/mol. X is selected from the group consisting of CRR′, SiRR′, C═O, N—R, B—R, O, S, SO, SO₂, and Se. R, R′, R₂, R_(x), R_(a), R_(b), and R_(c) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and any two adjacent substituents are optionally joined to form a ring, which may be further substituted. n is 1 or 2.

In one embodiment, n is 2. In one embodiment, n is 1. In one embodiment, X is O. In one, embodiment X is S. In one embodiment, R₁ contains at least 2 carbons. In one embodiment, R₁ contains at least 3 carbons.

In one embodiment, R₁ is independently selected from the group consisting of: ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, and cyclohexyl, wherein each group is optionally partially or fully deuterated.

In one embodiment, R₁ contains at least one deuterium.

In one embodiment, R_(c) comprises at least one chemical group selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, and fluorine.

In one embodiment, the compound has the formula:

In one embodiment, the compound has the formula:

wherein R₃, R₆ and R₇ represent mono, di, tri, tetra substitutions or no substitution, wherein R₃, R₄, R₅, R₆ and R₇ are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein two adjacent substituents of R₃, R₆ and R₇ are optionally joined to form a ring and may be further substituted; and wherein at least one of R₄ and R₅ is not hydrogen or deuterium.

In one embodiment, the compound has the formula:

In one embodiment, both R₄ and R₅ are not hydrogen or deuterium. In one embodiment, both R₄ and R₅ are alkyl or cycloalkyl. In one embodiment, both R₄ and R₅ are aryl or heteroaryl.

In one embodiment, the compound has the formula:

wherein Y₁ to Y₄ is CR₈ or N, and wherein each R₈ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein any two adjacent substituents of R₈ are optionally joined to form a ring and may be further substituted.

In one embodiment, the compound has the formula:

wherein R₃, R₆ and R₇ represent mono, di, tri, tetra substitutions or no substitution, wherein R₃, R₄, R₅, R₆ and R₇ are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein two adjacent substituents of R₃, R₆ and R₇ are optionally joined to form a ring and may be further substituted; and wherein at least one of R₄ and R₅ is not hydrogen or deuterium.

In one embodiment, the compound has the formula:

In one embodiment, the compound has the formula:

wherein R₁₂, R₁₃ and R₁₄ represent mono, di, tri, tetra substitutions or no substitution, wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, wherein two adjacent substituents of R₁₂, R₁₃ and R₁₄ are optionally joined to form a ring and may be further substituted; and wherein at least one of R₁₀ and R₁₁ is not hydrogen or deuterium.

In one embodiment, the compound has the formula:

In one embodiment, both R₁₀ and R₁₁ are not hydrogen or deuterium. In one embodiment, both R₁₀ and R₁₁ are alkyl or cycloalkyl. In one embodiment, both R₁₀ and R₁₁ are aryl or heteroaryl.

In one embodiment, the compound has the formula:

wherein Y₁ to Y₄ is CR₈ or N, and wherein each R₈ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein any two adjacent substituents of R₈ are optionally joined to form a ring and may be further substituted.

In one embodiment, the compound has the formula:

In one embodiment, the compound is selected from the group consisting of:

wherein X is O or S and Z is O or S. R₁ is selected from the group consisting of methyl-d3, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, and cyclohexyl, wherein each group is optionally partially or fully deuterated.

R₄, R₅, R₁₀, R₁₁, R₂₁ and R₂₂ are each independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and combinations thereof, and wherein each group is optionally partially or fully deuterated.

In one embodiment, the compound has the formula:

wherein R₁, R₄, and R₅ are alkyl.

In one embodiment, R₁, R₄, and R₅ are iso-propyl.

In one embodiment, R₁ is methyl-d3.

In one embodiment a first device is provided. The first device comprises an organic light emitting device, further comprising an anode, a cathode, and an organic layer, disposed between the anode and the cathode, comprising a compound having the formula:

is provided.

R₂, R_(x), R_(a), and R_(b), represent mono, di, tri, tetra substitutions or no substitution, and R₁ is an alkyl or cycloalkyl with a molecular weight higher than 15.5 g/mol. X is selected from the group consisting of CRR′, SiRR′, C═O, N—R, B—R, O, S, SO, SO₂, and Se. R, R′, R₂, R_(x), R_(a), R_(b), and R_(c) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and any two adjacent substituents are optionally joined to form a ring, which may be further substituted. n is 1 or 2.

In one embodiment, the organic layer is an emissive layer and the compound is an emissive dopant.

In one embodiment, the organic layer further comprises a host.

In one embodiment, the host comprises at least one of the chemical groups selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

The “aza” designation in the fragments described above, i.e. aza-dibenzofuran, aza-dibenzonethiophene, etc. means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[fh]quinoxaline and dibenzo[fh]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.

In one embodiment, the host is a metal complex.

In one embodiment, the host is a metal carbene complex.

In one embodiment, the metal carbene complex is selected from the group consisting of:

The term “metal carbene complex,” as used herein to refer to a metal coordination complex comprising at least one carbene ligand.

In one embodiment, the device further comprises a second organic layer that is a non-emissive layer between anode and the emissive layer; and wherein the material in the second organic layer is a metal carbene complex.

In one embodiment, the device further comprises a third organic layer that is a non-emissive layer between cathode and the emissive layer; and wherein the material in the third organic layer is a metal carbene complex.

In one embodiment, the device further comprises a second organic layer that is a non-emissive layer and the compound of Formula I is a material in the second organic layer.

In one embodiment, the second organic layer is a hole transporting layer and the compound of Formula I is a transporting material in the second organic layer.

In one embodiment, the second organic layer is a blocking layer and the compound having Formula I is a blocking material in the second organic layer.

In one embodiment, the first device is an organic light-emitting device.

In one embodiment, the first device is a consumer product.

In one embodiment, the first device comprises a lighting panel.

In one embodiment, a first device is provided. The first device comprising an organic light emitting device, further comprising an anode, a cathode, a first layer disposed between the anode and the cathode, and a second layer disposed between the first layer and the cathode, wherein the first layer is an emissive layer comprising an emissive dopant and a host and the second layer is a non-emissive layer comprising a first metal carbene complex.

In one embodiment, the host is a second metal carbene complex.

In one embodiment, the host is an organic compound.

In one embodiment, the device further comprises a third layer disposed between anode and the first layer; and wherein the third layer that is a non-emissive layer comprises a third metal carbene complex.

In one embodiment, the second layer is a hole blocking layer.

In one embodiment, the second layer is an exciton blocking layer.

In one embodiment, the second layer is an electron transporting layer.

In one embodiment, the third layer is an electron blocking layer.

In one embodiment, the third layer is an exciton blocking layer.

In one embodiment, the third layer is a hole transporting layer.

In one embodiment, the first layer further comprises a non-emissive dopant, and wherein the non-emissive dopant is a fourth metal-carbene complex.

In one embodiment, the emissive dopant is a fifth metal-carbene complex.

In one embodiment, the second metal carbene complex is the first metal carbene complex.

In one embodiment, the materials deposited between the anode and the cathode comprises essentially metal carbene complexes.

In one embodiment, the first metal carbene complex has the formula:

wherein M is a metal having an atomic number greater than 40. A₁, A₂ are each independently selected from the group consisting of C or N. A and B are each independently a 5 or 6-membered carbocyclic or heterocyclic ring. R_(A) and R_(B) represent mono, di, tri, or tetra substitutions or no substitution, and X is selected from the group consisting of NR_(C), PR_(C), O, and S. Each of R_(A), R_(B), and R_(C) are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein any two adjacent substituents are optionally joined together to form a ring, which may be further substituted. The ligand L is another ligand coordinated to the metal M, wherein m is a value from 1 to the maximum number of ligands that may be attached to the metal, and wherein m+n is the maximum number of ligands that may be attached to metal M.

In one embodiment, the metal is Ir or Pt.

In one embodiment, X is NR_(C).

In one embodiment, R_(B) is a fused heterocyclic ring; wherein the heteroatom in the fused heterocyclic ring is N; and wherein the fused heterocyclic ring is optionally further substituted.

In one embodiment, R_(A) is an electron withdrawing group with Hammett constant larger than 0. For general definition of Hammett constant, please see C. Hansch, et. al. Chem. Rev. 1991, 91, 165-195.

In one embodiment, the first metal carbene complex is selected from the group consisting of:

In one embodiment, the first device is an organic light-emitting device.

In one embodiment, the first device is a consumer product.

In one embodiment, the first device comprises a lighting panel.

In one embodiment, the compounds have the composition in Formula IV below:

Formula IV Compd. n X R_(x) R₁ R₂ R₃ R₄═R₅ R₆ R₇ 1. 1 O H Ethyl H H Methyl H H 2. 1 O H Ethyl H H Isopropyl H H 3. 1 O H Ethyl H H Isobutyl H H 4. 1 O H Ethyl H H Cyclohexyl H H 5. 1 O H Ethyl H H Ph H H 6. 1 O H Ethyl H H Methyl 4-isopropyl H 7. 1 O H Ethyl H H Isopropyl 4- H isopropyl 8. 1 O H Ethyl H H Isobutyl 4- H isopropyl 9. 1 O H Ethyl H H Cyclohexyl 4- H isopropyl 10. 1 O H Ethyl H H Ph 4- H isopropyl 11. 1 O H Ethyl H H Methyl 4-phenyl H 12. 1 O H Ethyl H H Isopropyl 4-phenyl H 13. 1 O H Ethyl H H Isobutyl 4-phenyl H 14. 1 O H Ethyl H H Cyclohexyl 4-phenyl H 15. 1 O H Ethyl H H Ph 4-phenyl H 16. 1 O H Isopropyl H H Methyl H H 17. 1 O H Isopropyl H H Isopropyl H H 18. 1 O H Isopropyl H H Isobutyl H H 19. 1 O H Isopropyl H H Cyclohexyl H H 20. 1 O H Isopropyl H H Ph H H 21. 1 O H Isopropyl H H Methyl 4- H isopropyl 22. 1 O H Isopropyl H H Isopropyl 4- H isopropyl 23. 1 O H Isopropyl H H Isobutyl 4- H isopropyl 24. 1 O H Isopropyl H H Cyclohexyl 4- H isopropyl 25. 1 O H Isopropyl H H Ph 4- H isopropyl 26. 1 O H Isopropyl H H Methyl 4-phenyl H 27. 1 O H Isopropyl H H Isopropyl 4-phenyl H 28. 1 O H Isopropyl H H Isobutyl 4-phenyl H 29. 1 O H Isopropyl H H Cyclohexyl 4-phenyl H 30. 1 O H Isopropyl H H Ph 4-phenyl H 31. 1 O H Isobutyl H H Methyl H H 32. 1 O H Isobutyl H H Isopropyl H H 33. 1 O H Isobutyl H H Isobutyl H H 34. 1 O H Isobutyl H H Cyclohexyl H H 35. 1 O H Isobutyl H H Ph H H 36. 1 O H Isobutyl H H Methyl 4- H isopropyl 37. 1 O H Isobutyl H H Isopropyl 4- H isopropyl 38. 1 O H Isobutyl H H Isobutyl 4- H isopropyl 39. 1 O H Isobutyl H H Cyclohexyl 4- H isopropyl 40. 1 O H Isobutyl H H Ph 4- H isopropyl 41. 1 O H Isobutyl H H Methyl 4-phenyl H 42. 1 O H Isobutyl H H Isopropyl 4-phenyl H 43. 1 O H Isobutyl H H Isobutyl 4-phenyl H 44. 1 O H Isobutyl H H Cyclohexyl 4-phenyl H 45. 1 O H Isobutyl H H Ph 4-phenyl H 46. 1 O H Cyclohexyl H H Methyl H H 47. 1 O H Cyclohexyl H H Isopropyl H H 48. 1 O H Cyclohexyl H H Isobutyl H H 49. 1 O H Cyclohexyl H H Cyclohexyl H H 50. 1 O H Cyclohexyl H H Ph H H 51. 1 O H Cyclohexyl H H Methyl 4- H isopropyl 52. 1 O H Cyclohexyl H H Isopropyl 4- H isopropyl 53. 1 O H Cyclohexyl H H Isobutyl 4- H isopropyl 54. 1 O H Cyclohexyl H H Cyclohexyl 4- H isopropyl 55. 1 O H Cyclohexyl H H Ph 4- H isopropyl 56. 1 O H Cyclohexyl H H Methyl 4-phenyl H 57. 1 O H Cyclohexyl H H Isopropyl 4-phenyl H 58. 1 O H Cyclohexyl H H Isobutyl 4-phenyl H 59. 1 O H Cyclohexyl H H Cyclohexyl 4-phenyl H 60. 1 O H Cyclohexyl H H Ph 4-phenyl H 61. 1 O H CD₃ H H Methyl H H 62. 1 O H CD₃ H H Isopropyl H H 63. 1 O H CD₃ H H Isobutyl H H 64. 1 O H CD₃ H H Cyclohexyl H H 65. 1 O H CD₃ H H Ph H H 66. 1 O H CD₃ H H Methyl 4- H isopropyl 67. 1 O H CD₃ H H Isopropyl 4- H isopropyl 68. 1 O H CD₃ H H Isobutyl 4- H isopropyl 69. 1 O H CD₃ H H Cyclohexyl 4- H isopropyl 70. 1 O H CD₃ H H Ph 4- H isopropyl 71. 1 O H CD₃ H H Methyl 4-phenyl H 72. 1 O H CD₃ H H Isopropyl 4-phenyl H 73. 1 O H CD₃ H H Isobutyl 4-phenyl H 74. 1 O H CD₃ H H Cyclohexyl 4-phenyl H 75. 1 O H CD₃ H H Ph 4-phenyl H 76. 1 S H Ethyl H H Methyl H H 77. 1 S H Ethyl H H Isopropyl H H 78. 1 S H Ethyl H H Isobutyl H H 79. 1 S H Ethyl H H Cyclohexyl H H 80. 1 S H Ethyl H H Ph H H 81. 1 S H Ethyl H H Methyl 4- H isopropyl 82. 1 S H Ethyl H H Isopropyl 4- H isopropyl 83. 1 S H Ethyl H H Isobutyl 4- H isopropyl 84. 1 S H Ethyl H H Cyclohexyl 4- H isopropyl 85. 1 S H Ethyl H H Ph 4- H isopropyl 86. 1 S H Ethyl H H Methyl 4-phenyl H 87. 1 S H Ethyl H H Isopropyl 4-phenyl H 88. 1 S H Ethyl H H Isobutyl 4-phenyl H 89. 1 S H Ethyl H H Cyclohexyl 4-phenyl H 90. 1 S H Ethyl H H Ph 4-phenyl H 91. 1 S H Isopropyl H H Methyl H H 92. 1 S H Isopropyl H H Isopropyl H H 93. 1 S H Isopropyl H H Isobutyl H H 94. 1 S H Isopropyl H H Cyclohexyl H H 95. 1 S H Isopropyl H H Ph H H 96. 1 S H Isopropyl H H Methyl 4- H isopropyl 97. 1 S H Isopropyl H H Isopropyl 4- H isopropyl 98. 1 S H Isopropyl H H Isobutyl 4- H isopropyl 99. 1 S H Isopropyl H H Cyclohexyl 4- H isopropyl 100. 1 S H Isopropyl H H Ph 4- H isopropyl 101. 1 S H Isopropyl H H Methyl 4-phenyl H 102. 1 S H Isopropyl H H Isopropyl 4-phenyl H 103. 1 S H Isopropyl H H Isobutyl 4-phenyl H 104. 1 S H Isopropyl H H Cyclohexyl 4-phenyl H 105. 1 S H Isopropyl H H Ph 4-phenyl H 106. 1 S H Isobutyl H H Methyl H H 107. 1 S H Isobutyl H H Isopropyl H H 108. 1 S H Isobutyl H H Isobutyl H H 109. 1 S H Isobutyl H H Cyclohexyl H H 110. 1 S H Isobutyl H H Ph H H 111. 1 S H Isobutyl H H Methyl 4- H isopropyl 112. 1 S H Isobutyl H H Isopropyl 4- H isopropyl 113. 1 S H Isobutyl H H Isobutyl 4- H isopropyl 114. 1 S H Isobutyl H H Cyclohexyl 4- H isopropyl 115. 1 S H Isobutyl H H Ph 4- H isopropyl 116. 1 S H Isobutyl H H Methyl 4-phenyl H 117. 1 S H Isobutyl H H Isopropyl 4-phenyl H 118. 1 S H Isobutyl H H Isobutyl 4-phenyl H 119. 1 S H Isobutyl H H Cyclohexyl 4-phenyl H 120. 1 S H Isobutyl H H Ph 4-phenyl H 121. 1 S H Cyclohexyl H H Methyl H H 122. 1 S H Cyclohexyl H H Isopropyl H H 123. 1 S H Cyclohexyl H H Isobutyl H H 124. 1 S H Cyclohexyl H H Cyclohexyl H H 125. 1 S H Cyclohexyl H H Ph H H 126. 1 S H Cyclohexyl H H Methyl 4- H isopropyl 127. 1 S H Cyclohexyl H H Isopropyl 4- H isopropyl 128. 1 S H Cyclohexyl H H Isobutyl 4- H isopropyl 129. 1 S H Cyclohexyl H H Cyclohexyl 4- H isopropyl 130. 1 S H Cyclohexyl H H Ph 4- H isopropyl 131. 1 S H Cyclohexyl H H Methyl 4-phenyl H 132. 1 S H Cyclohexyl H H Isopropyl 4-phenyl H 133. 1 S H Cyclohexyl H H Isobutyl 4-phenyl H 134. 1 S H Cyclohexyl H H Cyclohexyl 4-phenyl H 135. 1 S H Cyclohexyl H H Ph 4-phenyl H 136. 1 S H CD₃ H H Methyl H H 137. 1 S H CD₃ H H Isopropyl H H 138. 1 S H CD₃ H H Isobutyl H H 139. 1 S H CD₃ H H Cyclohexyl H H 140. 1 S H CD₃ H H Ph H H 141. 1 S H CD₃ H H Methyl 4- H isopropyl 142. 1 S H CD₃ H H Isopropyl 4- H isopropyl 143. 1 S H CD₃ H H Isobutyl 4- H isopropyl 144. 1 S H CD₃ H H Cyclohexyl 4- H isopropyl 145. 1 S H CD₃ H H Ph 4- H isopropyl 146. 1 S H CD₃ H H Methyl 4-phenyl H 147. 1 S H CD₃ H H Isopropyl 4-phenyl H 148. 1 S H CD₃ H H Isobutyl 4-phenyl H 149. 1 S H CD₃ H H Cyclohexyl 4-phenyl H 150. 1 S H CD₃ H H Ph 4-phenyl H 151. 2 O H Ethyl H H Methyl H H 152. 2 O H Ethyl H H Isopropyl H H 153. 2 O H Ethyl H H Isobutyl H H 154. 2 O H Ethyl H H Cyclohexyl H H 155. 2 O H Ethyl H H Ph H H 156. 2 O H Ethyl H H Methyl 4- H isopropyl 157. 2 O H Ethyl H H Isopropyl 4- H isopropyl 158. 2 O H Ethyl H H Isobutyl 4- H isopropyl 159. 2 O H Ethyl H H Cyclohexyl 4- H isopropyl 160. 2 O H Ethyl H H Ph 4- H isopropyl 161. 2 O H Ethyl H H Methyl 4-phenyl H 162. 2 O H Ethyl H H Isopropyl 4-phenyl H 163. 2 O H Ethyl H H Isobutyl 4-phenyl H 164. 2 O H Ethyl H H Cyclohexyl 4-phenyl H 165. 2 O H Ethyl H H Ph 4-phenyl H 166. 2 O H Isopropyl H H Methyl H H 167. 2 O H Isopropyl H H Isopropyl H H 168. 2 O H Isopropyl H H Isobutyl H H 169. 2 O H Isopropyl H H Cyclohexyl H H 170. 2 O H Isopropyl H H Ph H H 171. 2 O H Isopropyl H H Methyl 4- H isopropyl 172. 2 O H Isopropyl H H Isopropyl 4- H isopropyl 173. 2 O H Isopropyl H H Isobutyl 4- H isopropyl 174. 2 O H Isopropyl H H Cyclohexyl 4- H isopropyl 175. 2 O H Isopropyl H H Ph 4- H isopropyl 176. 2 O H Isopropyl H H Methyl 4-phenyl H 177. 2 O H Isopropyl H H Isopropyl 4-phenyl H 178. 2 O H Isopropyl H H Isobutyl 4-phenyl H 179. 2 O H Isopropyl H H Cyclohexyl 4-phenyl H 180. 2 O H Isopropyl H H Ph 4-phenyl H 181. 2 O H Isobutyl H H Methyl H H 182. 2 O H Isobutyl H H Isopropyl H H 183. 2 O H Isobutyl H H Isobutyl H H 184. 2 O H Isobutyl H H Cyclohexyl H H 185. 2 O H Isobutyl H H Ph H H 186. 2 O H Isobutyl H H Methyl 4- H isopropyl 187. 2 O H Isobutyl H H Isopropyl 4- H isopropyl 188. 2 O H Isobutyl H H Isobutyl 4- H isopropyl 189. 2 O H Isobutyl H H Cyclohexyl 4- H isopropyl 190. 2 O H Isobutyl H H Ph 4- H isopropyl 191. 2 O H Isobutyl H H Methyl 4-phenyl H 192. 2 O H Isobutyl H H Isopropyl 4-phenyl H 193. 2 O H Isobutyl H H Isobutyl 4-phenyl H 194. 2 O H Isobutyl H H Cyclohexyl 4-phenyl H 195. 2 O H Isobutyl H H Ph 4-phenyl H 196. 2 O H Cyclohexyl H H Methyl H H 197. 2 O H Cyclohexyl H H Isopropyl H H 198. 2 O H Cyclohexyl H H Isobutyl H H 199. 2 O H Cyclohexyl H H Cyclohexyl H H 200. 2 O H Cyclohexyl H H Ph H H 201. 2 O H Cyclohexyl H H Methyl 4- H isopropyl 202. 2 O H Cyclohexyl H H Isopropyl 4- H isopropyl 203. 2 O H Cyclohexyl H H Isobutyl 4- H isopropyl 204. 2 O H Cyclohexyl H H Cyclohexyl 4- H isopropyl 205. 2 O H Cyclohexyl H H Ph 4- H isopropyl 206. 2 O H Cyclohexyl H H Methyl 4-phenyl H 207. 2 O H Cyclohexyl H H Isopropyl 4-phenyl H 208. 2 O H Cyclohexyl H H Isobutyl 4-phenyl H 209. 2 O H Cyclohexyl H H Cyclohexyl 4-phenyl H 210. 2 O H Cyclohexyl H H Ph 4-phenyl H 211. 2 O H CD₃ H H Methyl H H 212. 2 O H CD₃ H H Isopropyl H H 213. 2 O H CD₃ H H Isobutyl H H 214. 2 O H CD₃ H H Cyclohexyl H H 215. 2 O H CD₃ H H Ph H H 216. 2 O H CD₃ H H Methyl 4- H isopropyl 217. 2 O H CD₃ H H Isopropyl 4- H isopropyl 218. 2 O H CD₃ H H Isobutyl 4- H isopropyl 219. 2 O H CD₃ H H Cyclohexyl 4- H isopropyl 220. 2 O H CD₃ H H Ph 4- H isopropyl 221. 2 O H CD₃ H H Methyl 4-phenyl H 222. 2 O H CD₃ H H Isopropyl 4-phenyl H 223. 2 O H CD₃ H H Isobutyl 4-phenyl H 224. 2 O H CD₃ H H Cyclohexyl 4-phenyl H 225. 2 O H CD₃ H H Ph 4-phenyl H 226. 2 S H Ethyl H H Methyl H H 227. 2 S H Ethyl H H Isopropyl H H 228. 2 S H Ethyl H H Isobutyl H H 229. 2 S H Ethyl H H Cyclohexyl H H 230. 2 S H Ethyl H H Ph H H 231. 2 S H Ethyl H H Methyl 4- H isopropyl 232. 2 S H Ethyl H H Isopropyl 4- H isopropyl 233. 2 S H Ethyl H H Isobutyl 4- H isopropyl 234. 2 S H Ethyl H H Cyclohexyl 4- H isopropyl 235. 2 S H Ethyl H H Ph 4- H isopropyl 236. 2 S H Ethyl H H Methyl 4-phenyl H 237. 2 S H Ethyl H H Isopropyl 4-phenyl H 238. 2 S H Ethyl H H Isobutyl 4-phenyl H 239. 2 S H Ethyl H H Cyclohexyl 4-phenyl H 240. 2 S H Ethyl H H Ph 4-phenyl H 241. 2 S H Isopropyl H H Methyl H H 242. 2 S H Isopropyl H H Isopropyl H H 243. 2 S H Isopropyl H H Isobutyl H H 244. 2 S H Isopropyl H H Cyclohexyl H H 245. 2 S H Isopropyl H H Ph H H 246. 2 S H Isopropyl H H Methyl 4- H isopropyl 247. 2 S H Isopropyl H H Isopropyl 4- H isopropyl 248. 2 S H Isopropyl H H Isobutyl 4- H isopropyl 249. 2 S H Isopropyl H H Cyclohexyl 4- H isopropyl 250. 2 S H Isopropyl H H Ph 4- H isopropyl 251. 2 S H Isopropyl H H Methyl 4-phenyl H 252. 2 S H Isopropyl H H Isopropyl 4-phenyl H 253. 2 S H Isopropyl H H Isobutyl 4-phenyl H 254. 2 S H Isopropyl H H Cyclohexyl 4-phenyl H 255. 2 S H Isopropyl H H Ph 4-phenyl H 256. 2 S H Isobutyl H H Methyl H H 257. 2 S H Isobutyl H H Isopropyl H H 258. 2 S H Isobutyl H H Isobutyl H H 259. 2 S H Isobutyl H H Cyclohexyl H H 260. 2 S H Isobutyl H H Ph H H 261. 2 S H Isobutyl H H Methyl 4- H isopropyl 262. 2 S H Isobutyl H H Isopropyl 4- H isopropyl 263. 2 S H Isobutyl H H Isobutyl 4- H isopropyl 264. 2 S H Isobutyl H H Cyclohexyl 4- H isopropyl 265. 2 S H Isobutyl H H Ph 4- H isopropyl 266. 2 S H Isobutyl H H Methyl 4-phenyl H 267. 2 S H Isobutyl H H Isopropyl 4-phenyl H 268. 2 S H Isobutyl H H Isobutyl 4-phenyl H 269. 2 S H Isobutyl H H Cyclohexyl 4-phenyl H 270. 2 S H Isobutyl H H Ph 4-phenyl H 271. 2 S H Cyclohexyl H H Methyl H H 272. 2 S H Cyclohexyl H H Isopropyl H H 273. 2 S H Cyclohexyl H H Isobutyl H H 274. 2 S H Cyclohexyl H H Cyclohexyl H H 275. 2 S H Cyclohexyl H H Ph H H 276. 2 S H Cyclohexyl H H Methyl 4- H isopropyl 277. 2 S H Cyclohexyl H H Isopropyl 4- H isopropyl 278. 2 S H Cyclohexyl H H Isobutyl 4- H isopropyl 279. 2 S H Cyclohexyl H H Cyclohexyl 4- H isopropyl 280. 2 S H Cyclohexyl H H Ph 4- H isopropyl 281. 2 S H Cyclohexyl H H Methyl 4-phenyl H 282. 2 S H Cyclohexyl H H Isopropyl 4-phenyl H 283. 2 S H Cyclohexyl H H Isobutyl 4-phenyl H 284. 2 S H Cyclohexyl H H Cyclohexyl 4-phenyl H 285. 2 S H Cyclohexyl H H Ph 4-phenyl H 286. 2 S H CD₃ H H Methyl H H 287. 2 S H CD₃ H H Isopropyl H H 288. 2 S H CD₃ H H Isobutyl H H 289. 2 S H CD₃ H H Cyclohexyl H H 290. 2 S H CD₃ H H Ph H H 291. 2 S H CD₃ H H Methyl 4- H isopropyl 292. 2 S H CD₃ H H Isopropyl 4- H isopropyl 293. 2 S H CD₃ H H Isobutyl 4- H isopropyl 294. 2 S H CD₃ H H Cyclohexyl 4- H isopropyl 295. 2 S H CD₃ H H Ph 4- H isopropyl 296. 2 S H CD₃ H H Methyl 4-phenyl H 297. 2 S H CD₃ H H Isopropyl 4-phenyl H 298. 2 S H CD₃ H H Isobutyl 4-phenyl H 299. 2 S H CD₃ H H Cyclohexyl 4-phenyl H 300. 2 S H CD₃ H H Ph 4-phenyl H

In one embodiment, the compounds have the composition in Formula XII below:

Formula XII Compd. n X R_(x) R₁ R₃ R₈ R₄═R₅ R₆ R₇ 301. 1 O H Ethyl H H Methyl H H 302. 1 O H Ethyl H H Isopropyl H H 303. 1 O H Ethyl H H Isobutyl H H 304. 1 O H Ethyl H H Cyclohexyl H H 305. 1 O H Ethyl H H Ph H H 306. 1 O H Ethyl H H Methyl 4- H isopropyl 307. 1 O H Ethyl H H Isopropyl 4- H isopropyl 308. 1 O H Ethyl H H Isobutyl 4- H isopropyl 309. 1 O H Ethyl H H Cyclohexyl 4- H isopropyl 310. 1 O H Ethyl H H Ph 4- H isopropyl 311. 1 O H Ethyl H H Methyl 4-phenyl H 312. 1 O H Ethyl H H Isopropyl 4-phenyl H 313. 1 O H Ethyl H H Isobutyl 4-phenyl H 314. 1 O H Ethyl H H Cyclohexyl 4-phenyl H 315. 1 O H Ethyl H H Ph 4-phenyl H 316. 1 O H Isopropyl H H Methyl H H 317. 1 O H Isopropyl H H Isopropyl H H 318. 1 O H Isopropyl H H Isobutyl H H 319. 1 O H Isopropyl H H Cyclohexyl H H 320. 1 O H Isopropyl H H Ph H H 321. 1 O H Isopropyl H H Methyl 4- H isopropyl 322. 1 O H Isopropyl H H Isopropyl 4- H isopropyl 323. 1 O H Isopropyl H H Isobutyl 4- H isopropyl 324. 1 O H Isopropyl H H Cyclohexyl 4- H isopropyl 325. 1 O H Isopropyl H H Ph 4- H isopropyl 326. 1 O H Isopropyl H H Methyl 4-phenyl H 327. 1 O H Isopropyl H H Isopropyl 4-phenyl H 328. 1 O H Isopropyl H H Isobutyl 4-phenyl H 329. 1 O H Isopropyl H H Cyclohexyl 4-phenyl H 330. 1 O H Isopropyl H H Ph 4-phenyl H 331. 1 O H Isobutyl H H Methyl H H 332. 1 O H Isobutyl H H Isopropyl H H 333. 1 O H Isobutyl H H Isobutyl H H 334. 1 O H Isobutyl H H Cyclohexyl H H 335. 1 O H Isobutyl H H Ph H H 336. 1 O H Isobutyl H H Methyl 4- H isopropyl 337. 1 O H Isobutyl H H Isopropyl 4- H isopropyl 338. 1 O H Isobutyl H H Isobutyl 4- H isopropyl 339. 1 O H Isobutyl H H Cyclohexyl 4- H isopropyl 340. 1 O H Isobutyl H H Ph 4- H isopropyl 341. 1 O H Isobutyl H H Methyl 4-phenyl H 342. 1 O H Isobutyl H H Isopropyl 4-phenyl H 343. 1 O H Isobutyl H H Isobutyl 4-phenyl H 344. 1 O H Isobutyl H H Cyclohexyl 4-phenyl H 345. 1 O H Isobutyl H H Ph 4-phenyl H 346. 1 O H Cyclohexyl H H Methyl H H 347. 1 O H Cyclohexyl H H Isopropyl H H 348. 1 O H Cyclohexyl H H Isobutyl H H 349. 1 O H Cyclohexyl H H Cyclohexyl H H 350. 1 O H Cyclohexyl H H Ph H H 351. 1 O H Cyclohexyl H H Methyl 4- H isopropyl 352. 1 O H Cyclohexyl H H Isopropyl 4- H isopropyl 353. 1 O H Cyclohexyl H H Isobutyl 4- H isopropyl 354. 1 O H Cyclohexyl H H Cyclohexyl 4- H isopropyl 355. 1 O H Cyclohexyl H H Ph 4- H isopropyl 356. 1 O H Cyclohexyl H H Methyl 4-phenyl H 357. 1 O H Cyclohexyl H H Isopropyl 4-phenyl H 358. 1 O H Cyclohexyl H H Isobutyl 4-phenyl H 359. 1 O H Cyclohexyl H H Cyclohexyl 4-phenyl H 360. 1 O H Cyclohexyl H H Ph 4-phenyl H 361. 1 O H CD₃ H H Methyl H H 362. 1 O H CD₃ H H Isopropyl H H 363. 1 O H CD₃ H H Isobutyl H H 364. 1 O H CD₃ H H Cyclohexyl H H 365. 1 O H CD₃ H H Ph H H 366. 1 O H CD₃ H H Methyl 4- H isopropyl 367. 1 O H CD₃ H H Isopropyl 4- H isopropyl 368. 1 O H CD₃ H H Isobutyl 4- H isopropyl 369. 1 O H CD₃ H H Cyclohexyl 4- H isopropyl 370. 1 O H CD₃ H H Ph 4- H isopropyl 371. 1 O H CD₃ H H Methyl 4-phenyl H 372. 1 O H CD₃ H H Isopropyl 4-phenyl H 373. 1 O H CD₃ H H Isobutyl 4-phenyl H 374. 1 O H CD₃ H H Cyclohexyl 4-phenyl H 375. 1 O H CD₃ H H Ph 4-phenyl H 376. 1 S H Ethyl H H Methyl H H 377. 1 S H Ethyl H H Isopropyl H H 378. 1 S H Ethyl H H Isobutyl H H 379. 1 S H Ethyl H H Cyclohexyl H H 380. 1 S H Ethyl H H Ph H H 381. 1 S H Ethyl H H Methyl 4- H isopropyl 382. 1 S H Ethyl H H Isopropyl 4- H isopropyl 383. 1 S H Ethyl H H Isobutyl 4- H isopropyl 384. 1 S H Ethyl H H Cyclohexyl 4- H isopropyl 385. 1 S H Ethyl H H Ph 4- H isopropyl 386. 1 S H Ethyl H H Methyl 4-phenyl H 387. 1 S H Ethyl H H Isopropyl 4-phenyl H 388. 1 S H Ethyl H H Isobutyl 4-phenyl H 389. 1 S H Ethyl H H Cyclohexyl 4-phenyl H 390. 1 S H Ethyl H H Ph 4-phenyl H 391. 1 S H Isopropyl H H Methyl H H 392. 1 S H Isopropyl H H Isopropyl H H 393. 1 S H Isopropyl H H Isobutyl H H 394. 1 S H Isopropyl H H Cyclohexyl H H 395. 1 S H Isopropyl H H Ph H H 396. 1 S H Isopropyl H H Methyl 4- H isopropyl 397. 1 S H Isopropyl H H Isopropyl 4- H isopropyl 398. 1 S H Isopropyl H H Isobutyl 4- H isopropyl 399. 1 S H Isopropyl H H Cyclohexyl 4- H isopropyl 400. 1 S H Isopropyl H H Ph 4- H isopropyl 401. 1 S H Isopropyl H H Methyl 4-phenyl H 402. 1 S H Isopropyl H H Isopropyl 4-phenyl H 403. 1 S H Isopropyl H H Isobutyl 4-phenyl H 404. 1 S H Isopropyl H H Cyclohexyl 4-phenyl H 405. 1 S H Isopropyl H H Ph 4-phenyl H 406. 1 S H Isobutyl H H Methyl H H 407. 1 S H Isobutyl H H Isopropyl H H 408. 1 S H Isobutyl H H Isobutyl H H 409. 1 S H Isobutyl H H Cyclohexyl H H 410. 1 S H Isobutyl H H Ph H H 411. 1 S H Isobutyl H H Methyl 4- H isopropyl 412. 1 S H Isobutyl H H Isopropyl 4- H isopropyl 413. 1 S H Isobutyl H H Isobutyl 4- H isopropyl 414. 1 S H Isobutyl H H Cyclohexyl 4- H isopropyl 415. 1 S H Isobutyl H H Ph 4- H isopropyl 416. 1 S H Isobutyl H H Methyl 4-phenyl H 417. 1 S H Isobutyl H H Isopropyl 4-phenyl H 418. 1 S H Isobutyl H H Isobutyl 4-phenyl H 419. 1 S H Isobutyl H H Cyclohexyl 4-phenyl H 420. 1 S H Isobutyl H H Ph 4-phenyl H 421. 1 S H Cyclohexyl H H Methyl H H 422. 1 S H Cyclohexyl H H Isopropyl H H 423. 1 S H Cyclohexyl H H Isobutyl H H 424. 1 S H Cyclohexyl H H Cyclohexyl H H 425. 1 S H Cyclohexyl H H Ph H H 426. 1 S H Cyclohexyl H H Methyl 4- H isopropyl 427. 1 S H Cyclohexyl H H Isopropyl 4- H isopropyl 428. 1 S H Cyclohexyl H H Isobutyl 4- H isopropyl 429. 1 S H Cyclohexyl H H Cyclohexyl 4- H isopropyl 430. 1 S H Cyclohexyl H H Ph 4- H isopropyl 431. 1 S H Cyclohexyl H H Methyl 4-phenyl H 432. 1 S H Cyclohexyl H H Isopropyl 4-phenyl H 433. 1 S H Cyclohexyl H H Isobutyl 4-phenyl H 434. 1 S H Cyclohexyl H H Cyclohexyl 4-phenyl H 435. 1 S H Cyclohexyl H H Ph 4-phenyl H 436. 1 S H CD₃ H H Methyl H H 437. 1 S H CD₃ H H Isopropyl H H 438. 1 S H CD₃ H H Isobutyl H H 439. 1 S H CD₃ H H Cyclohexyl H H 440. 1 S H CD₃ H H Ph H H 441. 1 S H CD₃ H H Methyl 4- H isopropyl 442. 1 S H CD₃ H H Isopropyl 4- H isopropyl 443. 1 S H CD₃ H H Isobutyl 4- H isopropyl 444. 1 S H CD₃ H H Cyclohexyl 4- H isopropyl 445. 1 S H CD₃ H H Ph 4- H isopropyl 446. 1 S H CD₃ H H Methyl 4-phenyl H 447. 1 S H CD₃ H H Isopropyl 4-phenyl H 448. 1 S H CD₃ H H Isobutyl 4-phenyl H 449. 1 S H CD₃ H H Cyclohexyl 4-phenyl H 450. 1 S H CD₃ H H Ph 4-phenyl H 451. 2 O H Ethyl H H Methyl H H 452. 2 O H Ethyl H H Isopropyl H H 453. 2 O H Ethyl H H Isobutyl H H 454. 2 O H Ethyl H H Cyclohexyl H H 455. 2 O H Ethyl H H Ph H H 456. 2 O H Ethyl H H Methyl 4- H isopropyl 457. 2 O H Ethyl H H Isopropyl 4- H isopropyl 458. 2 O H Ethyl H H Isobutyl 4- H isopropyl 459. 2 O H Ethyl H H Cyclohexyl 4- H isopropyl 460. 2 O H Ethyl H H Ph 4- H isopropyl 461. 2 O H Ethyl H H Methyl 4-phenyl H 462. 2 O H Ethyl H H Isopropyl 4-phenyl H 463. 2 O H Ethyl H H Isobutyl 4-phenyl H 464. 2 O H Ethyl H H Cyclohexyl 4-phenyl H 465. 2 O H Ethyl H H Ph 4-phenyl H 466. 2 O H Isopropyl H H Methyl H H 467. 2 O H Isopropyl H H Isopropyl H H 468. 2 O H Isopropyl H H Isobutyl H H 469. 2 O H Isopropyl H H Cyclohexyl H H 470. 2 O H Isopropyl H H Ph H H 471. 2 O H Isopropyl H H Methyl 4- H isopropyl 472. 2 O H Isopropyl H H Isopropyl 4- H isopropyl 473. 2 O H Isopropyl H H Isobutyl 4- H isopropyl 474. 2 O H Isopropyl H H Cyclohexyl 4- H isopropyl 475. 2 O H Isopropyl H H Ph 4- H isopropyl 476. 2 O H Isopropyl H H Methyl 4-phenyl H 477. 2 O H Isopropyl H H Isopropyl 4-phenyl H 478. 2 O H Isopropyl H H Isobutyl 4-phenyl H 479. 2 O H Isopropyl H H Cyclohexyl 4-phenyl H 480. 2 O H Isopropyl H H Ph 4-phenyl H 481. 2 O H Isobutyl H H Methyl H H 482. 2 O H Isobutyl H H Isopropyl H H 483. 2 O H Isobutyl H H Isobutyl H H 484. 2 O H Isobutyl H H Cyclohexyl H H 485. 2 O H Isobutyl H H Ph H H 486. 2 O H Isobutyl H H Methyl 4- H isopropyl 487. 2 O H Isobutyl H H Isopropyl 4- H isopropyl 488. 2 O H Isobutyl H H Isobutyl 4- H isopropyl 489. 2 O H Isobutyl H H Cyclohexyl 4- H isopropyl 490. 2 O H Isobutyl H H Ph 4- H isopropyl 491. 2 O H Isobutyl H H Methyl 4-phenyl H 492. 2 O H Isobutyl H H Isopropyl 4-phenyl H 493. 2 O H Isobutyl H H Isobutyl 4-phenyl H 494. 2 O H Isobutyl H H Cyclohexyl 4-phenyl H 495. 2 O H Isobutyl H H Ph 4-phenyl H 496. 2 O H Cyclohexyl H H Methyl H H 497. 2 O H Cyclohexyl H H Isopropyl H H 498. 2 O H Cyclohexyl H H Isobutyl H H 499. 2 O H Cyclohexyl H H Cyclohexyl H H 500. 2 O H Cyclohexyl H H Ph H H 501. 2 O H Cyclohexyl H H Methyl 4- H isopropyl 502. 2 O H Cyclohexyl H H Isopropyl 4- H isopropyl 503. 2 O H Cyclohexyl H H Isobutyl 4- H isopropyl 504. 2 O H Cyclohexyl H H Cyclohexyl 4- H isopropyl 505. 2 O H Cyclohexyl H H Ph 4- H isopropyl 506. 2 O H Cyclohexyl H H Methyl 4-phenyl H 507. 2 O H Cyclohexyl H H Isopropyl 4-phenyl H 508. 2 O H Cyclohexyl H H Isobutyl 4-phenyl H 509. 2 O H Cyclohexyl H H Cyclohexyl 4-phenyl H 510. 2 O H Cyclohexyl H H Ph 4-phenyl H 511. 2 O H CD₃ H H Methyl H H 512. 2 O H CD₃ H H Isopropyl H H 513. 2 O H CD₃ H H Isobutyl H H 514. 2 O H CD₃ H H Cyclohexyl H H 515. 2 O H CD₃ H H Ph H H 516. 2 O H CD₃ H H Methyl 4- H isopropyl 517. 2 O H CD₃ H H Isopropyl 4- H isopropyl 518. 2 O H CD₃ H H Isobutyl 4- H isopropyl 519. 2 O H CD₃ H H Cyclohexyl 4- H isopropyl 520. 2 O H CD₃ H H Ph 4- H isopropyl 521. 2 O H CD₃ H H Methyl 4-phenyl H 522. 2 O H CD₃ H H Isopropyl 4-phenyl H 523. 2 O H CD₃ H H Isobutyl 4-phenyl H 524. 2 O H CD₃ H H Cyclohexyl 4-phenyl H 525. 2 O H CD₃ H H Ph 4-phenyl H 526. 2 S H Ethyl H H Methyl H H 527. 2 S H Ethyl H H Isopropyl H H 528. 2 S H Ethyl H H Isobutyl H H 529. 2 S H Ethyl H H Cyclohexyl H H 530. 2 S H Ethyl H H Ph H H 531. 2 S H Ethyl H H Methyl 4- H isopropyl 532. 2 S H Ethyl H H Isopropyl 4- H isopropyl 533. 2 S H Ethyl H H Isobutyl 4- H isopropyl 534. 2 S H Ethyl H H Cyclohexyl 4- H isopropyl 535. 2 S H Ethyl H H Ph 4- H isopropyl 536. 2 S H Ethyl H H Methyl 4-phenyl H 537. 2 S H Ethyl H H Isopropyl 4-phenyl H 538. 2 S H Ethyl H H Isobutyl 4-phenyl H 539. 2 S H Ethyl H H Cyclohexyl 4-phenyl H 540. 2 S H Ethyl H H Ph 4-phenyl H 541. 2 S H Isopropyl H H Methyl H H 542. 2 S H Isopropyl H H Isopropyl H H 543. 2 S H Isopropyl H H Isobutyl H H 544. 2 S H Isopropyl H H Cyclohexyl H H 545. 2 S H Isopropyl H H Ph H H 546. 2 S H Isopropyl H H Methyl 4- H isopropyl 547. 2 S H Isopropyl H H Isopropyl 4- H isopropyl 548. 2 S H Isopropyl H H Isobutyl 4- H isopropyl 549. 2 S H Isopropyl H H Cyclohexyl 4- H isopropyl 550. 2 S H Isopropyl H H Ph 4- H isopropyl 551. 2 S H Isopropyl H H Methyl 4-phenyl H 552. 2 S H Isopropyl H H Isopropyl 4-phenyl H 553. 2 S H Isopropyl H H Isobutyl 4-phenyl H 554. 2 S H Isopropyl H H Cyclohexyl 4-phenyl H 555. 2 S H Isopropyl H H Ph 4-phenyl H 556. 2 S H Isobutyl H H Methyl H H 557. 2 S H Isobutyl H H Isopropyl H H 558. 2 S H Isobutyl H H Isobutyl H H 559. 2 S H Isobutyl H H Cyclohexyl H H 560. 2 S H Isobutyl H H Ph H H 561. 2 S H Isobutyl H H Methyl 4- H isopropyl 562. 2 S H Isobutyl H H Isopropyl 4- H isopropyl 563. 2 S H Isobutyl H H Isobutyl 4- H isopropyl 564. 2 S H Isobutyl H H Cyclohexyl 4- H isopropyl 565. 2 S H Isobutyl H H Ph 4- H isopropyl 566. 2 S H Isobutyl H H Methyl 4-phenyl H 567. 2 S H Isobutyl H H Isopropyl 4-phenyl H 568. 2 S H Isobutyl H H Isobutyl 4-phenyl H 569. 2 S H Isobutyl H H Cyclohexyl 4-phenyl H 570. 2 S H Isobutyl H H Ph 4-phenyl H 571. 2 S H Cyclohexyl H H Methyl H H 572. 2 S H Cyclohexyl H H Isopropyl H H 573. 2 S H Cyclohexyl H H Isobutyl H H 574. 2 S H Cyclohexyl H H Cyclohexyl H H 575. 2 S H Cyclohexyl H H Ph H H 576. 2 S H Cyclohexyl H H Methyl 4- H isopropyl 577. 2 S H Cyclohexyl H H Isopropyl 4- H isopropyl 578. 2 S H Cyclohexyl H H Isobutyl 4- H isopropyl 579. 2 S H Cyclohexyl H H Cyclohexyl 4- H isopropyl 580. 2 S H Cyclohexyl H H Ph 4- H isopropyl 581. 2 S H Cyclohexyl H H Methyl 4-phenyl H 582. 2 S H Cyclohexyl H H Isopropyl 4-phenyl H 583. 2 S H Cyclohexyl H H Isobutyl 4-phenyl H 584. 2 S H Cyclohexyl H H Cyclohexyl 4-phenyl H 585. 2 S H Cyclohexyl H H Ph 4-phenyl H 586. 2 S H CD₃ H H Methyl H H 587. 2 S H CD₃ H H Isopropyl H H 588. 2 S H CD₃ H H Isobutyl H H 589. 2 S H CD₃ H H Cyclohexyl H H 590. 2 S H CD₃ H H Ph H H 591. 2 S H CD₃ H H Methyl 4- H isopropyl 592. 2 S H CD₃ H H Isopropyl 4- H isopropyl 593. 2 S H CD₃ H H Isobutyl 4- H isopropyl 594. 2 S H CD₃ H H Cyclohexyl 4- H isopropyl 595. 2 S H CD₃ H H Ph 4- H isopropyl 596. 2 S H CD₃ H H Methyl 4-phenyl H 597. 2 S H CD₃ H H Isopropyl 4-phenyl H 598. 2 S H CD₃ H H Isobutyl 4-phenyl H 599. 2 S H CD₃ H H Cyclohexyl 4-phenyl H 600. 2 S H CD₃ H H Ph 4-phenyl H

In one embodiment, the compounds have the composition of Formula IX below:

Formula IX Compd. n X R_(x) R₁ R₂ R₉ R₁₀═R₁₁ R₁₄ R₁₂═R₁₃ 601. 1 O H Ethyl H H Methyl H H 602. 1 O H Ethyl H H Isopropyl H H 603. 1 O H Ethyl H H Isobutyl H H 604. 1 O H Ethyl H H Cyclohexyl H H 605. 1 O H Ethyl H H Ph H H 606. 1 O H Ethyl H H Methyl 4- H isopropyl 607. 1 O H Ethyl H H Isopropyl 4- H isopropyl 608. 1 O H Ethyl H H Isobutyl 4- H isopropyl 609. 1 O H Ethyl H H Cyclohexyl 4- H isopropyl 610. 1 O H Ethyl H H Ph 4- H isopropyl 611. 1 O H Ethyl H H Methyl 4-phenyl H 612. 1 O H Ethyl H H Isopropyl 4-phenyl H 613. 1 O H Ethyl H H Isobutyl 4-phenyl H 614. 1 O H Ethyl H H Cyclohexyl 4-phenyl H 615. 1 O H Ethyl H H Ph 4-phenyl H 616. 1 O H Isopropyl H H Methyl H H 617. 1 O H Isopropyl H H Isopropyl H H 618. 1 O H Isopropyl H H Isobutyl H H 619. 1 O H Isopropyl H H Cyclohexyl H H 620. 1 O H Isopropyl H H Ph H H 621. 1 O H Isopropyl H H Methyl 4- H isopropyl 622. 1 O H Isopropyl H H Isopropyl 4- H isopropyl 623. 1 O H Isopropyl H H Isobutyl 4- H isopropyl 624. 1 O H Isopropyl H H Cyclohexyl 4- H isopropyl 625. 1 O H Isopropyl H H Ph 4- H isopropyl 626. 1 O H Isopropyl H H Methyl 4-phenyl H 627. 1 O H Isopropyl H H Isopropyl 4-phenyl H 628. 1 O H Isopropyl H H Isobutyl 4-phenyl H 629. 1 O H Isopropyl H H Cyclohexyl 4-phenyl H 630. 1 O H Isopropyl H H Ph 4-phenyl H 631. 1 O H Isobutyl H H Methyl H H 632. 1 O H Isobutyl H H Isopropyl H H 633. 1 O H Isobutyl H H Isobutyl H H 634. 1 O H Isobutyl H H Cyclohexyl H H 635. 1 O H Isobutyl H H Ph H H 636. 1 O H Isobutyl H H Methyl 4- H isopropyl 637. 1 O H Isobutyl H H Isopropyl 4- H isopropyl 638. 1 O H Isobutyl H H Isobutyl 4- H isopropyl 639. 1 O H Isobutyl H H Cyclohexyl 4- H isopropyl 640. 1 O H Isobutyl H H Ph 4- H isopropyl 641. 1 O H Isobutyl H H Methyl 4-phenyl H 642. 1 O H Isobutyl H H Isopropyl 4-phenyl H 643. 1 O H Isobutyl H H Isobutyl 4-phenyl H 644. 1 O H Isobutyl H H Cyclohexyl 4-phenyl H 645. 1 O H Isobutyl H H Ph 4-phenyl H 646. 1 O H Cyclohexyl H H Methyl H H 647. 1 O H Cyclohexyl H H Isopropyl H H 648. 1 O H Cyclohexyl H H Isobutyl H H 649. 1 O H Cyclohexyl H H Cyclohexyl H H 650. 1 O H Cyclohexyl H H Ph H H 651. 1 O H Cyclohexyl H H Methyl 4- H isopropyl 652. 1 O H Cyclohexyl H H Isopropyl 4- H isopropyl 653. 1 O H Cyclohexyl H H Isobutyl 4- H isopropyl 654. 1 O H Cyclohexyl H H Cyclohexyl 4- H isopropyl 655. 1 O H Cyclohexyl H H Ph 4- H isopropyl 656. 1 O H Cyclohexyl H H Methyl 4-phenyl H 657. 1 O H Cyclohexyl H H Isopropyl 4-phenyl H 658. 1 O H Cyclohexyl H H Isobutyl 4-phenyl H 659. 1 O H Cyclohexyl H H Cyclohexyl 4-phenyl H 660. 1 O H Cyclohexyl H H Ph 4-phenyl H 661. 1 O H Cyclohexyl H H Methyl H H 662. 1 O H CD₃ H H Isopropyl H H 663. 1 O H CD₃ H H Isobutyl H H 664. 1 O H CD₃ H H Cyclohexyl H H 665. 1 O H CD₃ H H Ph H H 666. 1 O H CD₃ H H Methyl 4- H isopropyl 667. 1 O H CD₃ H H Isopropyl 4- H isopropyl 668. 1 O H CD₃ H H Isobutyl 4- H isopropyl 669. 1 O H CD₃ H H Cyclohexyl 4- H isopropyl 670. 1 O H CD₃ H H Ph 4- H isopropyl 671. 1 O H CD₃ H H Methyl 4-phenyl H 672. 1 O H CD₃ H H Isopropyl 4-phenyl H 673. 1 O H CD₃ H H Isobutyl 4-phenyl H 674. 1 O H CD₃ H H Cyclohexyl 4-phenyl H 675. 1 O H CD₃ H H Ph 4-phenyl H 676. 1 S H Ethyl H H Methyl H H 677. 1 S H Ethyl H H Isopropyl H H 678. 1 S H Ethyl H H Isobutyl H H 679. 1 S H Ethyl H H Cyclohexyl H H 680. 1 S H Ethyl H H Ph H H 681. 1 S H Ethyl H H Methyl 4- H isopropyl 682. 1 S H Ethyl H H Isopropyl 4- H isopropyl 683. 1 S H Ethyl H H Isobutyl 4- H isopropyl 684. 1 S H Ethyl H H Cyclohexyl 4- H isopropyl 685. 1 S H Ethyl H H Ph 4- H isopropyl 686. 1 S H Ethyl H H Methyl 4-phenyl H 687. 1 S H Ethyl H H Isopropyl 4-phenyl H 688. 1 S H Ethyl H H Isobutyl 4-phenyl H 689. 1 S H Ethyl H H Cyclohexyl 4-phenyl H 690. 1 S H Ethyl H H Ph 4-phenyl H 691. 1 S H Isopropyl H H Methyl H H 692. 1 S H Isopropyl H H Isopropyl H H 693. 1 S H Isopropyl H H Isobutyl H H 694. 1 S H Isopropyl H H Cyclohexyl H H 695. 1 S H Isopropyl H H Ph H H 696. 1 S H Isopropyl H H Methyl 4- H isopropyl 697. 1 S H Isopropyl H H Isopropyl 4- H isopropyl 698. 1 S H Isopropyl H H Isobutyl 4- H isopropyl 699. 1 S H Isopropyl H H Cyclohexyl 4- H isopropyl 700. 1 S H Isopropyl H H Ph 4- H isopropyl 701. 1 S H Isopropyl H H Methyl 4-phenyl H 702. 1 S H Isopropyl H H Isopropyl 4-phenyl H 703. 1 S H Isopropyl H H Isobutyl 4-phenyl H 704. 1 S H Isopropyl H H Cyclohexyl 4-phenyl H 705. 1 S H Isopropyl H H Ph 4-phenyl H 706. 1 S H Isobutyl H H Methyl H H 707. 1 S H Isobutyl H H Isopropyl H H 708. 1 S H Isobutyl H H Isobutyl H H 709. 1 S H Isobutyl H H Cyclohexyl H H 710. 1 S H Isobutyl H H Ph H H 711. 1 S H Isobutyl H H Methyl 4- H isopropyl 712. 1 S H Isobutyl H H Isopropyl 4- H isopropyl 713. 1 S H Isobutyl H H Isobutyl 4- H isopropyl 714. 1 S H Isobutyl H H Cyclohexyl 4- H isopropyl 715. 1 S H Isobutyl H H Ph 4- H isopropyl 716. 1 S H Isobutyl H H Methyl 4-phenyl H 717. 1 S H Isobutyl H H Isopropyl 4-phenyl H 718. 1 S H Isobutyl H H Isobutyl 4-phenyl H 719. 1 S H Isobutyl H H Cyclohexyl 4-phenyl H 720. 1 S H Isobutyl H H Ph 4-phenyl H 721. 1 S H Cyclohexyl H H Methyl H H 722. 1 S H Cyclohexyl H H Isopropyl H H 723. 1 S H Cyclohexyl H H Isobutyl H H 724. 1 S H Cyclohexyl H H Cyclohexyl H H 725. 1 S H Cyclohexyl H H Ph H H 726. 1 S H Cyclohexyl H H Methyl 4- H isopropyl 727. 1 S H Cyclohexyl H H Isopropyl 4- H isopropyl 728. 1 S H Cyclohexyl H H Isobutyl 4- H isopropyl 729. 1 S H Cyclohexyl H H Cyclohexyl 4- H isopropyl 730. 1 S H Cyclohexyl H H Ph 4- H isopropyl 731. 1 S H Cyclohexyl H H Methyl 4-phenyl H 732. 1 S H Cyclohexyl H H Isopropyl 4-phenyl H 733. 1 S H Cyclohexyl H H Isobutyl 4-phenyl H 734. 1 S H Cyclohexyl H H Cyclohexyl 4-phenyl H 735. 1 S H Cyclohexyl H H Ph 4-phenyl H 736. 1 S H CD₃ H H Methyl H H 737. 1 S H CD₃ H H Isopropyl H H 738. 1 S H CD₃ H H Isobutyl H H 739. 1 S H CD₃ H H Cyclohexyl H H 740. 1 S H CD₃ H H Ph H H 741. 1 S H CD₃ H H Methyl 4- H isopropyl 742. 1 S H CD₃ H H Isopropyl 4- H isopropyl 743. 1 S H CD₃ H H Isobutyl 4- H isopropyl 744. 1 S H CD₃ H H Cyclohexyl 4- H isopropyl 745. 1 S H CD₃ H H Ph 4- H isopropyl 746. 1 S H CD₃ H H Methyl 4-phenyl H 747. 1 S H CD₃ H H Isopropyl 4-phenyl H 748. 1 S H CD₃ H H Isobutyl 4-phenyl H 749. 1 S H CD₃ H H Cyclohexyl 4-phenyl H 750. 1 S H CD₃ H H Ph 4-phenyl H 751. 2 O H Ethyl H H Methyl H H 752. 2 O H Ethyl H H Isopropyl H H 753. 2 O H Ethyl H H Isobutyl H H 754. 2 O H Ethyl H H Cyclohexyl H H 755. 2 O H Ethyl H H Ph H H 756. 2 O H Ethyl H H Methyl 4- H isopropyl 757. 2 O H Ethyl H H Isopropyl 4- H isopropyl 758. 2 O H Ethyl H H Isobutyl 4- H isopropyl 759. 2 O H Ethyl H H Cyclohexyl 4- H isopropyl 760. 2 O H Ethyl H H Ph 4- H isopropyl 761. 2 O H Ethyl H H Methyl 4-phenyl H 762. 2 O H Ethyl H H Isopropyl 4-phenyl H 763. 2 O H Ethyl H H Isobutyl 4-phenyl H 764. 2 O H Ethyl H H Cyclohexyl 4-phenyl H 765. 2 O H Ethyl H H Ph 4-phenyl H 766. 2 O H Isopropyl H H Methyl H H 767. 2 O H Isopropyl H H Isopropyl H H 768. 2 O H Isopropyl H H Isobutyl H H 769. 2 O H Isopropyl H H Cyclohexyl H H 770. 2 O H Isopropyl H H Ph H H 771. 2 O H Isopropyl H H Methyl 4- H isopropyl 772. 2 O H Isopropyl H H Isopropyl 4- H isopropyl 773. 2 O H Isopropyl H H Isobutyl 4- H isopropyl 774. 2 O H Isopropyl H H Cyclohexyl 4- H isopropyl 775. 2 O H Isopropyl H H Ph 4- H isopropyl 776. 2 O H Isopropyl H H Methyl 4-phenyl H 777. 2 O H Isopropyl H H Isopropyl 4-phenyl H 778. 2 O H Isopropyl H H Isobutyl 4-phenyl H 779. 2 O H Isopropyl H H Cyclohexyl 4-phenyl H 780. 2 O H Isopropyl H H Ph 4-phenyl H 781. 2 O H Isobutyl H H Methyl H H 782. 2 O H Isobutyl H H Isopropyl H H 783. 2 O H Isobutyl H H Isobutyl H H 784. 2 O H Isobutyl H H Cyclohexyl H H 785. 2 O H Isobutyl H H Ph H H 786. 2 O H Isobutyl H H Methyl 4- H isopropyl 787. 2 O H Isobutyl H H Isopropyl 4- H isopropyl 788. 2 O H Isobutyl H H Isobutyl 4- H isopropyl 789. 2 O H Isobutyl H H Cyclohexyl 4- H isopropyl 790. 2 O H Isobutyl H H Ph 4- H isopropyl 791. 2 O H Isobutyl H H Methyl 4-phenyl H 792. 2 O H Isobutyl H H Isopropyl 4-phenyl H 793. 2 O H Isobutyl H H Isobutyl 4-phenyl H 794. 2 O H Isobutyl H H Cyclohexyl 4-phenyl H 795. 2 O H Isobutyl H H Ph 4-phenyl H 796. 2 O H Cyclohexyl H H Methyl H H 797. 2 O H Cyclohexyl H H Isopropyl H H 798. 2 O H Cyclohexyl H H Isobutyl H H 799. 2 O H Cyclohexyl H H Cyclohexyl H H 800. 2 O H Cyclohexyl H H Ph H H 801. 2 O H Cyclohexyl H H Methyl 4- H isopropyl 802. 2 O H Cyclohexyl H H Isopropyl 4- H isopropyl 803. 2 O H Cyclohexyl H H Isobutyl 4- H isopropyl 804. 2 O H Cyclohexyl H H Cyclohexyl 4- H isopropyl 805. 2 O H Cyclohexyl H H Ph 4- H isopropyl 806. 2 O H Cyclohexyl H H Methyl 4-phenyl H 807. 2 O H Cyclohexyl H H Isopropyl 4-phenyl H 808. 2 O H Cyclohexyl H H Isobutyl 4-phenyl H 809. 2 O H Cyclohexyl H H Cyclohexyl 4-phenyl H 810. 2 O H Cyclohexyl H H Ph 4-phenyl H 811. 2 O H CD₃ H H Methyl H H 812. 2 O H CD₃ H H Isopropyl H H 813. 2 O H CD₃ H H Isobutyl H H 814. 2 O H CD₃ H H Cyclohexyl H H 815. 2 O H CD₃ H H Ph H H 816. 2 O H CD₃ H H Methyl 4- H isopropyl 817. 2 O H CD₃ H H Isopropyl 4- H isopropyl 818. 2 O H CD₃ H H Isobutyl 4- H isopropyl 819. 2 O H CD₃ H H Cyclohexyl 4- H isopropyl 820. 2 O H CD₃ H H Ph 4- H isopropyl 821. 2 O H CD₃ H H Methyl 4-phenyl H 822. 2 O H CD₃ H H Isopropyl 4-phenyl H 823. 2 O H CD₃ H H Isobutyl 4-phenyl H 824. 2 O H CD₃ H H Cyclohexyl 4-phenyl H 825. 2 O H CD₃ H H Ph 4-phenyl H 826. 2 S H Ethyl H H Methyl H H 827. 2 S H Ethyl H H Isopropyl H H 828. 2 S H Ethyl H H Isobutyl H H 829. 2 S H Ethyl H H Cyclohexyl H H 830. 2 S H Ethyl H H Ph H H 831. 2 S H Ethyl H H Methyl 4- H isopropyl 832. 2 S H Ethyl H H Isopropyl 4- H isopropyl 833. 2 S H Ethyl H H Isobutyl 4- H isopropyl 834. 2 S H Ethyl H H Cyclohexyl 4- H isopropyl 835. 2 S H Ethyl H H Ph 4- H isopropyl 836. 2 S H Ethyl H H Methyl 4-phenyl H 837. 2 S H Ethyl H H Isopropyl 4-phenyl H 838. 2 S H Ethyl H H Isobutyl 4-phenyl H 839. 2 S H Ethyl H H Cyclohexyl 4-phenyl H 840. 2 S H Ethyl H H Ph 4-phenyl H 841. 2 S H Isopropyl H H Methyl H H 842. 2 S H Isopropyl H H Isopropyl H H 843. 2 S H Isopropyl H H Isobutyl H H 844. 2 S H Isopropyl H H Cyclohexyl H H 845. 2 S H Isopropyl H H Ph H H 846. 2 S H Isopropyl H H Methyl 4- H isopropyl 847. 2 S H Isopropyl H H Isopropyl 4- H isopropyl 848. 2 S H Isopropyl H H Isobutyl 4- H isopropyl 849. 2 S H Isopropyl H H Cyclohexyl 4- H isopropyl 850. 2 S H Isopropyl H H Ph 4- H isopropyl 851. 2 S H Isopropyl H H Methyl 4-phenyl H 852. 2 S H Isopropyl H H Isopropyl 4-phenyl H 853. 2 S H Isopropyl H H Isobutyl 4-phenyl H 854. 2 S H Isopropyl H H Cyclohexyl 4-phenyl H 855. 2 S H Isopropyl H H Ph 4-phenyl H 856. 2 S H Isobutyl H H Methyl H H 857. 2 S H Isobutyl H H Isopropyl H H 858. 2 S H Isobutyl H H Isobutyl H H 859. 2 S H Isobutyl H H Cyclohexyl H H 860. 2 S H Isobutyl H H Ph H H 861. 2 S H Isobutyl H H Methyl 4- H isopropyl 862. 2 S H Isobutyl H H Isopropyl 4- H isopropyl 863. 2 S H Isobutyl H H Isobutyl 4- H isopropyl 864. 2 S H Isobutyl H H Cyclohexyl 4- H isopropyl 865. 2 S H Isobutyl H H Ph 4- H isopropyl 866. 2 S H Isobutyl H H Methyl 4-phenyl H 867. 2 S H Isobutyl H H Isopropyl 4-phenyl H 868. 2 S H Isobutyl H H Isobutyl 4-phenyl H 869. 2 S H Isobutyl H H Cyclohexyl 4-phenyl H 870. 2 S H Isobutyl H H Ph 4-phenyl H 871. 2 S H Cyclohexyl H H Methyl H H 872. 2 S H Cyclohexyl H H Isopropyl H H 873. 2 S H Cyclohexyl H H Isobutyl H H 874. 2 S H Cyclohexyl H H Cyclohexyl H H 875. 2 S H Cyclohexyl H H Ph H H 876. 2 S H Cyclohexyl H H Methyl 4- H isopropyl 877. 2 S H Cyclohexyl H H Isopropyl 4- H isopropyl 878. 2 S H Cyclohexyl H H Isobutyl 4- H isopropyl 879. 2 S H Cyclohexyl H H Cyclohexyl 4- H isopropyl 880. 2 S H Cyclohexyl H H Ph 4- H isopropyl 881. 2 S H Cyclohexyl H H Methyl 4-phenyl H 882. 2 S H Cyclohexyl H H Isopropyl 4-phenyl H 883. 2 S H Cyclohexyl H H Isobutyl 4-phenyl H 884. 2 S H Cyclohexyl H H Cyclohexyl 4-phenyl H 885. 2 S H Cyclohexyl H H Ph 4-phenyl H 886. 2 S H CD₃ H H Methyl H H 887. 2 S H CD₃ H H Isopropyl H H 888. 2 S H CD₃ H H Isobutyl H H 889. 2 S H CD₃ H H Cyclohexyl H H 890. 2 S H CD₃ H H Ph H H 891. 2 S H CD₃ H H Methyl 4- H isopropyl 892. 2 S H CD₃ H H Isopropyl 4- H isopropyl 893. 2 S H CD₃ H H Isobutyl 4- H isopropyl 894. 2 S H CD₃ H H Cyclohexyl 4- H isopropyl 895. 2 S H CD₃ H H Ph 4- H isopropyl 896. 2 S H CD₃ H H Methyl 4-phenyl H 897. 2 S H CD₃ H H Isopropyl 4-phenyl H 898. 2 S H CD₃ H H Isobutyl 4-phenyl H 899. 2 S H CD₃ H H Cyclohexyl 4-phenyl H 900. 2 S H CD₃ H H Ph 4-phenyl H

In one embodiment, the compounds have the composition of Formula XIII below:

Formula XIII Compd. n X R_(x) R₁ R₈ R₉ R₁₀═R₁₁ R₁₄ R₁₂═R₁₃ 901. 1 O H Ethyl H H Methyl H H 902. 1 O H Ethyl H H Isopropyl H H 903. 1 O H Ethyl H H Isobutyl H H 904. 1 O H Ethyl H H Cyclohexyl H H 905. 1 O H Ethyl H H Ph H H 906. 1 O H Ethyl H H Methyl 4- H isopropyl 907. 1 O H Ethyl H H Isopropyl 4- H isopropyl 908. 1 O H Ethyl H H Isobutyl 4- H isopropyl 909. 1 O H Ethyl H H Cyclohexyl 4- H isopropyl 910. 1 O H Ethyl H H Ph 4- H isopropyl 911. 1 O H Ethyl H H Methyl 4-phenyl H 912. 1 O H Ethyl H H Isopropyl 4-phenyl H 913. 1 O H Ethyl H H Isobutyl 4-phenyl H 914. 1 O H Ethyl H H Cyclohexyl 4-phenyl H 915. 1 O H Ethyl H H Ph 4-phenyl H 916. 1 O H Isopropyl H H Methyl H H 917. 1 O H Isopropyl H H Isopropyl H H 918. 1 O H Isopropyl H H Isobutyl H H 919. 1 O H Isopropyl H H Cyclohexyl H H 920. 1 O H Isopropyl H H Ph H H 921. 1 O H Isopropyl H H Methyl 4- H isopropyl 922. 1 O H Isopropyl H H Isopropyl 4- H isopropyl 923. 1 O H Isopropyl H H Isobutyl 4- H isopropyl 924. 1 O H Isopropyl H H Cyclohexyl 4- H isopropyl 925. 1 O H Isopropyl H H Ph 4- H isopropyl 926. 1 O H Isopropyl H H Methyl 4-phenyl H 927. 1 O H Isopropyl H H Isopropyl 4-phenyl H 928. 1 O H Isopropyl H H Isobutyl 4-phenyl H 929. 1 O H Isopropyl H H Cyclohexyl 4-phenyl H 930. 1 O H Isopropyl H H Ph 4-phenyl H 931. 1 O H Isobutyl H H Methyl H H 932. 1 O H Isobutyl H H Isopropyl H H 933. 1 O H Isobutyl H H Isobutyl H H 934. 1 O H Isobutyl H H Cyclohexyl H H 935. 1 O H Isobutyl H H Ph H H 936. 1 O H Isobutyl H H Methyl 4- H isopropyl 937. 1 O H Isobutyl H H Isopropyl 4- H isopropyl 938. 1 O H Isobutyl H H Isobutyl 4- H isopropyl 939. 1 O H Isobutyl H H Cyclohexyl 4- H isopropyl 940. 1 O H Isobutyl H H Ph 4- H isopropyl 941. 1 O H Isobutyl H H Methyl 4-phenyl H 942. 1 O H Isobutyl H H Isopropyl 4-phenyl H 943. 1 O H Isobutyl H H Isobutyl 4-phenyl H 944. 1 O H Isobutyl H H Cyclohexyl 4-phenyl H 945. 1 O H Isobutyl H H Ph 4-phenyl H 946. 1 O H Cyclohexyl H H Methyl H H 947. 1 O H Cyclohexyl H H Isopropyl H H 948. 1 O H Cyclohexyl H H Isobutyl H H 949. 1 O H Cyclohexyl H H Cyclohexyl H H 950. 1 O H Cyclohexyl H H Ph H H 951. 1 O H Cyclohexyl H H Methyl 4- H isopropyl 952. 1 O H Cyclohexyl H H Isopropyl 4- H isopropyl 953. 1 O H Cyclohexyl H H Isobutyl 4- H isopropyl 954. 1 O H Cyclohexyl H H Cyclohexyl 4- H isopropyl 955. 1 O H Cyclohexyl H H Ph 4- H isopropyl 956. 1 O H Cyclohexyl H H Methyl 4-phenyl H 957. 1 O H Cyclohexyl H H Isopropyl 4-phenyl H 958. 1 O H Cyclohexyl H H Isobutyl 4-phenyl H 959. 1 O H Cyclohexyl H H Cyclohexyl 4-phenyl H 960. 1 O H Cyclohexyl H H Ph 4-phenyl H 961. 1 O H CD₃ H H Methyl H H 962. 1 O H CD₃ H H Isopropyl H H 963. 1 O H CD₃ H H Isobutyl H H 964. 1 O H CD₃ H H Cyclohexyl H H 965. 1 O H CD₃ H H Ph H H 966. 1 O H CD₃ H H Methyl 4- H isopropyl 967. 1 O H CD₃ H H Isopropyl 4- H isopropyl 968. 1 O H CD₃ H H Isobutyl 4- H isopropyl 969. 1 O H CD₃ H H Cyclohexyl 4- H isopropyl 970. 1 O H CD₃ H H Ph 4- H isopropyl 971. 1 O H CD₃ H H Methyl 4-phenyl H 972. 1 O H CD₃ H H Isopropyl 4-phenyl H 973. 1 O H CD₃ H H Isobutyl 4-phenyl H 974. 1 O H CD₃ H H Cyclohexyl 4-phenyl H 975. 1 O H CD₃ H H Ph 4-phenyl H 976. 1 S H Ethyl H H Methyl H H 977. 1 S H Ethyl H H Isopropyl H H 978. 1 S H Ethyl H H Isobutyl H H 979. 1 S H Ethyl H H Cyclohexyl H H 980. 1 S H Ethyl H H Ph H H 981. 1 S H Ethyl H H Methyl 4- H isopropyl 982. 1 S H Ethyl H H Isopropyl 4- H isopropyl 983. 1 S H Ethyl H H Isobutyl 4- H isopropyl 984. 1 S H Ethyl H H Cyclohexyl 4- H isopropyl 985. 1 S H Ethyl H H Ph 4- H isopropyl 986. 1 S H Ethyl H H Methyl 4-phenyl H 987. 1 S H Ethyl H H Isopropyl 4-phenyl H 988. 1 S H Ethyl H H Isobutyl 4-phenyl H 989. 1 S H Ethyl H H Cyclohexyl 4-phenyl H 990. 1 S H Ethyl H H Ph 4-phenyl H 991. 1 S H Isopropyl H H Methyl H H 992. 1 S H Isopropyl H H Isopropyl H H 993. 1 S H Isopropyl H H Isobutyl H H 994. 1 S H Isopropyl H H Cyclohexyl H H 995. 1 S H Isopropyl H H Ph H H 996. 1 S H Isopropyl H H Methyl 4- H isopropyl 997. 1 S H Isopropyl H H Isopropyl 4- H isopropyl 998. 1 S H Isopropyl H H Isobutyl 4- H isopropyl 999. 1 S H Isopropyl H H Cyclohexyl 4- H isopropyl 1000. 1 S H Isopropyl H H Ph 4- H isopropyl 1001. 1 S H Isopropyl H H Methyl 4-phenyl H 1002. 1 S H Isopropyl H H Isopropyl 4-phenyl H 1003. 1 S H Isopropyl H H Isobutyl 4-phenyl H 1004. 1 S H Isopropyl H H Cyclohexyl 4-phenyl H 1005. 1 S H Isopropyl H H Ph 4-phenyl H 1006. 1 S H Isobutyl H H Methyl H H 1007. 1 S H Isobutyl H H Isopropyl H H 1008. 1 S H Isobutyl H H Isobutyl H H 1009. 1 S H Isobutyl H H Cyclohexyl H H 1010. 1 S H Isobutyl H H Ph H H 1011. 1 S H Isobutyl H H Methyl 4- H isopropyl 1012. 1 S H Isobutyl H H Isopropyl 4- H isopropyl 1013. 1 S H Isobutyl H H Isobutyl 4- H isopropyl 1014. 1 S H Isobutyl H H Cyclohexyl 4- H isopropyl 1015. 1 S H Isobutyl H H Ph 4- H isopropyl 1016. 1 S H Isobutyl H H Methyl 4-phenyl H 1017. 1 S H Isobutyl H H Isopropyl 4-phenyl H 1018. 1 S H Isobutyl H H Isobutyl 4-phenyl H 1019. 1 S H Isobutyl H H Cyclohexyl 4-phenyl H 1020. 1 S H Isobutyl H H Ph 4-phenyl H 1021. 1 S H Cyclohexyl H H Methyl H H 1022. 1 S H Cyclohexyl H H Isopropyl H H 1023. 1 S H Cyclohexyl H H Isobutyl H H 1024. 1 S H Cyclohexyl H H Cyclohexyl H H 1025. 1 S H Cyclohexyl H H Ph H H 1026. 1 S H Cyclohexyl H H Methyl 4- H isopropyl 1027. 1 S H Cyclohexyl H H Isopropyl 4- H isopropyl 1028. 1 S H Cyclohexyl H H Isobutyl 4- H isopropyl 1029. 1 S H Cyclohexyl H H Cyclohexyl 4- H isopropyl 1030. 1 S H Cyclohexyl H H Ph 4- H isopropyl 1031. 1 S H Cyclohexyl H H Methyl 4-phenyl H 1032. 1 S H Cyclohexyl H H Isopropyl 4-phenyl H 1033. 1 S H Cyclohexyl H H Isobutyl 4-phenyl H 1034. 1 S H Cyclohexyl H H Cyclohexyl 4-phenyl H 1035. 1 S H Cyclohexyl H H Ph 4-phenyl H 1036. 1 S H CD₃ H H Methyl H H 1037. 1 S H CD₃ H H Isopropyl H H 1038. 1 S H CD₃ H H Isobutyl H H 1039. 1 S H CD₃ H H Cyclohexyl H H 1040. 1 S H CD₃ H H Ph H H 1041. 1 S H CD₃ H H Methyl 4- H isopropyl 1042. 1 S H CD₃ H H Isopropyl 4- H isopropyl 1043. 1 S H CD₃ H H Isobutyl 4- H isopropyl 1044. 1 S H CD₃ H H Cyclohexyl 4- H isopropyl 1045. 1 S H CD₃ H H Ph 4- H isopropyl 1046. 1 S H CD₃ H H Methyl 4-phenyl H 1047. 1 S H CD₃ H H Isopropyl 4-phenyl H 1048. 1 S H CD₃ H H Isobutyl 4-phenyl H 1049. 1 S H CD₃ H H Cyclohexyl 4-phenyl H 1050. 1 S H CD₃ H H Ph 4-phenyl H 1051. 2 O H Ethyl H H Methyl H H 1052. 2 O H Ethyl H H Isopropyl H H 1053. 2 O H Ethyl H H Isobutyl H H 1054. 2 O H Ethyl H H Cyclohexyl H H 1055. 2 O H Ethyl H H Ph H H 1056. 2 O H Ethyl H H Methyl 4- H isopropyl 1057. 2 O H Ethyl H H Isopropyl 4- H isopropyl 1058. 2 O H Ethyl H H Isobutyl 4- H isopropyl 1059. 2 O H Ethyl H H Cyclohexyl 4- H isopropyl 1060. 2 O H Ethyl H H Ph 4- H isopropyl 1061. 2 O H Ethyl H H Methyl 4-phenyl H 1062. 2 O H Ethyl H H Isopropyl 4-phenyl H 1063. 2 O H Ethyl H H Isobutyl 4-phenyl H 1064. 2 O H Ethyl H H Cyclohexyl 4-phenyl H 1065. 2 O H Ethyl H H Ph 4-phenyl H 1066. 2 O H Isopropyl H H Methyl H H 1067. 2 O H Isopropyl H H Isopropyl H H 1068. 2 O H Isopropyl H H Isobutyl H H 1069. 2 O H Isopropyl H H Cyclohexyl H H 1070. 2 O H Isopropyl H H Ph H H 1071. 2 O H Isopropyl H H Methyl 4- H isopropyl 1072. 2 O H Isopropyl H H Isopropyl 4- H isopropyl 1073. 2 O H Isopropyl H H Isobutyl 4- H isopropyl 1074. 2 O H Isopropyl H H Cyclohexyl 4- H isopropyl 1075. 2 O H Isopropyl H H Ph 4- H isopropyl 1076. 2 O H Isopropyl H H Methyl 4-phenyl H 1077. 2 O H Isopropyl H H Isopropyl 4-phenyl H 1078. 2 O H Isopropyl H H Isobutyl 4-phenyl H 1079. 2 O H Isopropyl H H Cyclohexyl 4-phenyl H 1080. 2 O H Isopropyl H H Ph 4-phenyl H 1081. 2 O H Isobutyl H H Methyl H H 1082. 2 O H Isobutyl H H Isopropyl H H 1083. 2 O H Isobutyl H H Isobutyl H H 1084. 2 O H Isobutyl H H Cyclohexyl H H 1085. 2 O H Isobutyl H H Ph H H 1086. 2 O H Isobutyl H H Methyl 4- H isopropyl 1087. 2 O H Isobutyl H H Isopropyl 4- H isopropyl 1088. 2 O H Isobutyl H H Isobutyl 4- H isopropyl 1089. 2 O H Isobutyl H H Cyclohexyl 4- H isopropyl 1090. 2 O H Isobutyl H H Ph 4- H isopropyl 1091. 2 O H Isobutyl H H Methyl 4-phenyl H 1092. 2 O H Isobutyl H H Isopropyl 4-phenyl H 1093. 2 O H Isobutyl H H Isobutyl 4-phenyl H 1094. 2 O H Isobutyl H H Cyclohexyl 4-phenyl H 1095. 2 O H Isobutyl H H Ph 4-phenyl H 1096. 2 O H Cyclohexyl H H Methyl H H 1097. 2 O H Cyclohexyl H H Isopropyl H H 1098. 2 O H Cyclohexyl H H Isobutyl H H 1099. 2 O H Cyclohexyl H H Cyclohexyl H H 1100. 2 O H Cyclohexyl H H Ph H H 1101. 2 O H Cyclohexyl H H Methyl 4- H isopropyl 1102. 2 O H Cyclohexyl H H Isopropyl 4- H isopropyl 1103. 2 O H Cyclohexyl H H Isobutyl 4- H isopropyl 1104. 2 O H Cyclohexyl H H Cyclohexyl 4- H isopropyl 1105. 2 O H Cyclohexyl H H Ph 4- H isopropyl 1106. 2 O H Cyclohexyl H H Methyl 4-phenyl H 1107. 2 O H Cyclohexyl H H Isopropyl 4-phenyl H 1108. 2 O H Cyclohexyl H H Isobutyl 4-phenyl H 1109. 2 O H Cyclohexyl H H Cyclohexyl 4-phenyl H 1110. 2 O H Cyclohexyl H H Ph 4-phenyl H 1111. 2 O H CD₃ H H Methyl H H 1112. 2 O H CD₃ H H Isopropyl H H 1113. 2 O H CD₃ H H Isobutyl H H 1114. 2 O H CD₃ H H Cyclohexyl H H 1115. 2 O H CD₃ H H Ph H H 1116. 2 O H CD₃ H H Methyl 4- H isopropyl 1117. 2 O H CD₃ H H Isopropyl 4- H isopropyl 1118. 2 O H CD₃ H H Isobutyl 4- H isopropyl 1119. 2 O H CD₃ H H Cyclohexyl 4- H isopropyl 1120. 2 O H CD₃ H H Ph 4- H isopropyl 1121. 2 O H CD₃ H H Methyl 4-phenyl H 1122. 2 O H CD₃ H H Isopropyl 4-phenyl H 1123. 2 O H CD₃ H H Isobutyl 4-phenyl H 1124. 2 O H CD₃ H H Cyclohexyl 4-phenyl H 1125. 2 O H CD₃ H H Ph 4-phenyl H 1126. 2 S H Ethyl H H Methyl H H 1127. 2 S H Ethyl H H Isopropyl H H 1128. 2 S H Ethyl H H Isobutyl H H 1129. 2 S H Ethyl H H Cyclohexyl H H 1130. 2 S H Ethyl H H Ph H H 1131. 2 S H Ethyl H H Methyl 4- H isopropyl 1132. 2 S H Ethyl H H Isopropyl 4- H isopropyl 1133. 2 S H Ethyl H H Isobutyl 4- H isopropyl 1134. 2 S H Ethyl H H Cyclohexyl 4- H isopropyl 1135. 2 S H Ethyl H H Ph 4- H isopropyl 1136. 2 S H Ethyl H H Methyl 4-phenyl H 1137. 2 S H Ethyl H H Isopropyl 4-phenyl H 1138. 2 S H Ethyl H H Isobutyl 4-phenyl H 1139. 2 S H Ethyl H H Cyclohexyl 4-phenyl H 1140. 2 S H Ethyl H H Ph 4-phenyl H 1141. 2 S H Isopropyl H H Methyl H H 1142. 2 S H Isopropyl H H Isopropyl H H 1143. 2 S H Isopropyl H H Isobutyl H H 1144. 2 S H Isopropyl H H Cyclohexyl H H 1145. 2 S H Isopropyl H H Ph H H 1146. 2 S H Isopropyl H H Methyl 4- H isopropyl 1147. 2 S H Isopropyl H H Isopropyl 4- H isopropyl 1148. 2 S H Isopropyl H H Isobutyl 4- H isopropyl 1149. 2 S H Isopropyl H H Cyclohexyl 4- H isopropyl 1150. 2 S H Isopropyl H H Ph 4- H isopropyl 1151. 2 S H Isopropyl H H Methyl 4-phenyl H 1152. 2 S H Isopropyl H H Isopropyl 4-phenyl H 1153. 2 S H Isopropyl H H Isobutyl 4-phenyl H 1154. 2 S H Isopropyl H H Cyclohexyl 4-phenyl H 1155. 2 S H Isopropyl H H Ph 4-phenyl H 1156. 2 S H Isobutyl H H Methyl H H 1157. 2 S H Isobutyl H H Isopropyl H H 1158. 2 S H Isobutyl H H Isobutyl H H 1159. 2 S H Isobutyl H H Cyclohexyl H H 1160. 2 S H Isobutyl H H Ph H H 1161. 2 S H Isobutyl H H Methyl 4- H isopropyl 1162. 2 S H Isobutyl H H Isopropyl 4- H isopropyl 1163. 2 S H Isobutyl H H Isobutyl 4- H isopropyl 1164. 2 S H Isobutyl H H Cyclohexyl 4- H isopropyl 1165. 2 S H Isobutyl H H Ph 4- H isopropyl 1166. 2 S H Isobutyl H H Methyl 4-phenyl H 1167. 2 S H Isobutyl H H Isopropyl 4-phenyl H 1168. 2 S H Isobutyl H H Isobutyl 4-phenyl H 1169. 2 S H Isobutyl H H Cyclohexyl 4-phenyl H 1170. 2 S H Isobutyl H H Ph 4-phenyl H 1171. 2 S H Cyclohexyl H H Methyl H H 1172. 2 S H Cyclohexyl H H Isopropyl H H 1173. 2 S H Cyclohexyl H H Isobutyl H H 1174. 2 S H Cyclohexyl H H Cyclohexyl H H 1175. 2 S H Cyclohexyl H H Ph H H 1176. 2 S H Cyclohexyl H H Methyl 4- H isopropyl 1177. 2 S H Cyclohexyl H H Isopropyl 4- H isopropyl 1178. 2 S H Cyclohexyl H H Isobutyl 4- H isopropyl 1179. 2 S H Cyclohexyl H H Cyclohexyl 4- H isopropyl 1180. 2 S H Cyclohexyl H H Ph 4- H isopropyl 1181. 2 S H Cyclohexyl H H Methyl 4-phenyl H 1182. 2 S H Cyclohexyl H H Isopropyl 4-phenyl H 1183. 2 S H Cyclohexyl H H Isobutyl 4-phenyl H 1184. 2 S H Cyclohexyl H H Cyclohexyl 4-phenyl H 1185. 2 S H Cyclohexyl H H Ph 4-phenyl H 1186. 2 S H CD₃ H H Methyl H H 1187. 2 S H CD₃ H H Isopropyl H H 1188. 2 S H CD₃ H H Isobutyl H H 1189. 2 S H CD₃ H H Cyclohexyl H H 1190. 2 S H CD₃ H H Ph H H 1191. 2 S H CD₃ H H Methyl 4- H isopropyl 1192. 2 S H CD₃ H H Isopropyl 4- H isopropyl 1193. 2 S H CD₃ H H Isobutyl 4- H isopropyl 1194. 2 S H CD₃ H H Cyclohexyl 4- H isopropyl 1195. 2 S H CD₃ H H Ph 4- H isopropyl 1196. 2 S H CD₃ H H Methyl 4-phenyl H 1197. 2 S H CD₃ H H Isopropyl 4-phenyl H 1198. 2 S H CD₃ H H Isobutyl 4-phenyl H 1199. 2 S H CD₃ H H Cyclohexyl 4-phenyl H 1200. 2 S H CD₃ H H Ph 4-phenyl H

Device Data:

All device examples were fabricated by high vacuum (<10⁻⁷ Torr) thermal evaporation (VTE). The anode electrode is 800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H₂O and O₂) immediately after fabrication, and a moisture getter was incorporated inside the package.

The organic stack of the device examples consisted of sequentially, from the ITO surface, 100 Å of LG101 (purchased from LG Chem) as the hole injection layer (HIL), 300 Å of 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD) or 2% Alq (tris-8-hydroxyquinoline aluminum) doped NPD as the hole transporting layer (HTL), 300 Å of 10-20 wt % of a compound of Formula I doped in Compound H as the emissive layer (EML), 50 Å blocking layer (BL), 350 Å Alq as the electron transport layer (ETL). The device results and data are summarized in Table 1 and Table 2 from those devices. As used herein, NPD, Alq, Compound A, and Compound H have the following structures:

TABLE 1 VTE Phosphorescent OLEDs Example HIL HTL EML (300 Å, doping %) BL ETL Comparative LG101 100 Å NPD 300 Å Compound H Compound A Compound H Alq 350 Å Example 1 15% 50 Å Comparative LG101 100 Å NPD: 2% Alq Compound H Compound A Compound H Alq 350 Å Example 2 300 Å 15% 50 Å Comparative LG101 100 Å NPD 300 Å Compound H Compound A Compound H Alq 350 Å Example 3 20% 50 Å Comparative LG101 100 Å NPD 300 Å Compound H Compound B Compound H Alq 350 Å Example 4 15% 50 Å Comparative LG101 100 Å NPD: 2% Alq Compound H Compound B Compound H Alq 350 Å Example 5 300 Å 15% 50 Å Comparative LG101 100 Å NPD: 2% Alq Compound H Compound B Compound H Alq 350 Å Example 6 300 Å 20% 50 Å Example 1 LG101 100 Å NPD 300 Å Compound H Compound 17 Compound H Alq 350 Å 15% 50 Å Example 2 LG101 100 Å NPD: 2% Alq Compound H Compound 17 Compound H Alq 350 Å 300 Å 15% 50 Å Example 3 LG101 100 Å NPD 300 Å Compound H Compound 17 Compound H Alq 350 Å 20% 50 Å Example 4 LG101 100 Å NPD: 2% Alq Compound H Compound 17 Compound H Alq 350 Å 300 Å 20% 50 Å Example 5 LG101 100 Å NPD: 2% Alq Compound H Compound 27 Compound H Alq 350 Å 300 Å 10% 50 Å Example 6 LG101 100 Å NPD 300 Å Compound H Compound 27 Compound H Alq 350 Å 15% 50 Å Example 7 LG101 100 Å NPD: 2% Alq Compound H Compound 27 Compound H Alq 350 Å 300 Å 10% 50 Å Example 8 LG101 100 Å NPD: 2% Alq Compound H Compound 27 Compound H Alq 350 Å 300 Å 20% 50 Å Example 9 LG101 100 Å NPD 300 Å Compound H Compound 62 Compound H Alq 350 Å 15% 50 Å Example 10 LG101 100 Å NPD: 2% Alq Compound H Compound 62 Compound H Alq 350 Å 300 Å 15% 50 Å Example 11 LG101 100 Å NPD: 2% Alq Compound H Compound 62 Compound H Alq 350 Å 300 Å 20% 50 Å

TABLE 2 VTE Device Data at 1000 nits λ_(max) FWHM Voltage LE EQE Example x y (nm) (nm) (V) (Cd/A) (%) LT80% (h) Comparative 0.158 0.276 464 53 5.7 27.7 15.1 116 Example 1 Comparative 0.159 0.281 464 54 5.7 26.8 14.4 184 Example 2 Comparative 0.157 0.273 464 53 5.2 27.3 14.9 116 Example 3 Comparative 0.156 0.290 466 59 6.0 26.3 13.6 162 Example 4 Comparative 0.159 0.276 464 54 6.0 22.9 12.4 194 Example 5 Comparative 0.158 0.304 466 60 5.5 27.2 13.9 150 Example 6 Example 1 0.155 0.257 464 52 5.3 23.3 13.2 152 Example 2 0.156 0.262 464 52 5.4 25.3 14.2 159 Example 3 0.153 0.261 464 52 4.8 26.7 15.1 139 Example 4 0.156 0.261 464 52 4.8 24.7 13.9 145 Example 5 0.161 0.280 464 54 6.2 24.9 13.3 241 Example 6 0.158 0.271 464 53 5.4 28.1 15.4 229 Example 7 0.160 0.275 464 54 5.3 29.6 16.1 251 Example 8 0.158 0.271 464 53 4.9 31.6 17.3 238 Example 9 0.155 0.287 466 57 5.7 26.6 14.2 199 Example 10 0.160 0.297 466 58 5.9 23.9 12.4 254 Example 11 0.156 0.271 464 54 5.3 22.7 12.5 181

The compounds of Formula I gave surprisingly unexpected properties. For example, comparative compounds Compound A and Compound B both have methyl substitution on the carbene nitrogen. Compounds of Formula I such as Compound 27 and 18 have isopropyl substitution on the carbene nitrogen. The sublimation temperatures for the compounds of Formula I were surprisingly smaller compared to the comparative compounds. Compound 27 sublimed under high vacuum at 300° C., which is 30 degrees lower than Compound A. Also, Compound 18 sublimed at 270° C., while Compound B evaporated at 290° C. It is desirable to lower the sublimation temperature since high temperature may cause decomposition of the compound, resulting in poor device performance. Since the sublimation temperature for a given class of compounds is normally proportional to the molecular weight of the compounds (i.e. the heavier the compound the higher the sublimation temperature), it is unexpected that the compounds of Formula I showed much lower sublimation temperatures although they have higher molecular weight.

Evaporation Compound Temperature (° C.) Compound A 330 Compound 27 300 Compound B 290 Compound 17 270

The device performance using the compounds of Formula I also showed improvement over the comparative compounds. For example, as shown in Tables 4 and 5, Compound 27 showed better efficiency, lower driving voltage, and longer device lifetime than Compound A. Both compounds showed blue emission with a λ_(max) at 464 nm and full width at half maximum (FWHM) of 54 nm. At 1000 nits, device with Compound 27 at 15% doping (Example 7) had an EQE of 16.1% at 5.3 V. At the same brightness, device with Compound A (Comparative Example 2) had an EQE of 14.4% at 5.7 V. The voltage was 0.4 V lower. In addition, the LT₈₀ was improved from 184 hours to 251 hours.

Compound 62 has a methyl-d3 substitution at the carbene nitrogen. Compared to Compound B, the devices with Compound 62 showed improved device performance as can be seen from device examples 9-11 and comparative examples 4-6. Devices with Compound 62 and Compound B showed similar CIE, driving voltage, and efficiency. However, devices with Compound 62 showed longer lifetime than Compound B. For example, LT80 of the devices improved from 162 hours to 199 hours for 15% doping with NPD HTL, from 194 hours to 254 hours for 15% doping with NPD:Alq HTL, and from 150 hours to 181 hours for 20% doping with NPD:Alq HTL.

TABLE 4 VTE device with carbene HBL, host, and EBL Example HIL HTL EBL EML (300 Å, doping %) HBL ETL Comparative LG101 NPD None Compound H4 Compound 27 Compound H 50 Å Alq 350 Å Example 7 100 Å 300 Å 15% Comparative LG101 NPD Compound C Compound H4 Compound 27 Compound H 50 Å Alq 350 Å Example 8 100 Å 270 Å 30 Å 15% Example 12 LG101 NPD Compound C Compound H4 Compound 27 Compound D 50 Å Alq 350 Å 100 Å 270 Å 30 Å 15% Example 13 LG101 NPD None Compound H4 Compound 27 Compound D 50 Å Alq 350 Å 100 Å 300 Å 15% Example 14 LG101 NPD None Compound H4 Compound 27 Compound D 50 Å Alq 350 Å 100 Å 300 Å (75%) 15% Compound D (10%)

TABLE 5 VTE device data at 1000 nits λ_(max) FWHM Voltage LE LT50% Example x y (nm) (nm) (V) (Cd/A) EQE (%) (Relative) Comparative 0.159 0.282 466 56 6.8 17.5 9.5 100 Example 7 Comparative 0.158 0.280 466 56 7.1 17.8 9.6 114 Example 8 Example 12 0.162 0.291 466 57 7.6 12.9 6.8 159 Example 13 0.160 0.289 466 57 7.4 14.3 7.6 132 Example 14 0.158 0.280 466 55 6.3 20.5 11.1 205

Carbene metal complexes have been used as electron blocking layer and host in OLEDs. On the other hand, it has been unexpectedly discovered that using carbene metal complexes in the hole blocking layer/electron transporting layer has not been reported. Device results showed the benefit of using such complexes as or in the hole blocking layer (HBL) in OLEDs.

As shown in Tables 4 and 5, device examples 12-14 had carbene complex Compound D as HBL whereas comparative examples 7 and 8 had Compound H as HBL. Device lifetime improvement was observed for device examples 12-14. With the same device structure, device example 12 showed 40% lifetime improvement over comparative example 8 (159 vs. 114). Device example 13 showed 30% lifetime improvement over comparative example 7 (132 vs. 100). When Compound D was used as a co-dopant in the emissive layer, it showed further benefit to the device. Not only did the device show higher efficiency (11.1% EQE) and lower driving voltage (6.3 V at 1000 nits), it also much longer lifetime (205).

Combination with Other Materials

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

HIL/HTL:

A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphryin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO_(x); a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the group consisting of:

k is an integer from 1 to 20; X¹ to X⁸ is C (including CH) or N; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:

M is a metal, having an atomic weight greater than 40; (Y¹—Y²) is a bidentate ligand, Y¹ and Y² are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y¹—Y²) is a 2-phenylpyridine derivative.

In another aspect, (Y¹—Y²) is a carbene ligand.

In another aspect, M is selected from Ir, Pt, Os, and Zn.

In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc⁺/Fc couple less than about 0.6 V.

Host:

The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have the following general formula:

M is a metal; (Y³—Y⁴) is a bidentate ligand, Y³ and Y⁴ are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:

(O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, M is selected from Ir and Pt.

In a further aspect, (Y³—Y⁴) is a carbene ligand.

Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, host compound contains at least one of the following groups in the molecule:

R¹ to R⁷ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.

k is an integer from 0 to 20.

X¹ to X⁸ is selected from C (including CH) or N.

Z¹ and Z² is selected from NR¹, O, or S.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.

In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of the following groups in the molecule:

k is an integer from 0 to 20; L is an ancillary ligand, m is an integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

In one aspect, compound used in ETL contains at least one of the following groups in the molecule:

R¹ is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.

Ar¹ to Ar³ has the similar definition as Ar's mentioned above.

k is an integer from 0 to 20.

X¹ to X⁸ is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:

(O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.

In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 6 below. Table 6 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.

TABLE 6 MATERIAL EXAMPLES OF MATERIAL PUBLICATIONS Hole injection materials Phthalocyanine and porphryin compounds

Appl. Phys. Lett. 69, 2160 (1996) Starburst triarylamines

J. Lumin. 72-74, 985 (1997) CF_(x) Fluorohydrocarbon polymer

Appl. Phys. Lett. 78, 673 (2001) Conducting polymers (e.g., PEDOT:PSS, polyaniline, polypthiophene)

Synth. Met. 87, 171 (1997) WO2007002683 Phosphonic acid and sliane SAMs

US20030162053 Triarylamine or polythiophene polymers with conductivity dopants

EP1725079A1

Organic compounds with conductive inorganic compounds, such as molybdenum and tungsten oxides

US20050123751 SID Symposium Digest, 37, 923 (2006) WO2009018009 n-type semiconducting organic complexes

US20020158242 Metal organometallic complexes

US20060240279 Cross-linkable compounds

US20080220265 Polythiophene based polymers and copolymers

WO 2011075644 EP2350216 Hole transporting materials Triarylamines (e.g., TPD, α-NPD)

Appl. Phys. Lett. 51, 913 (1987)

U.S. Pat. No. 5,061,569

EP650955

J. Mater. Chem. 3, 319 (1993)

Appl. Phys. Lett. 90, 183503 (2007)

Appl. Phys. Lett. 90, 183503 (2007) Triaylamine on spirofluorene core

Synth. Met. 91, 209 (1997) Arylamine carbazole compounds

Adv. Mater. 6, 677 (1994), US20080124572 Triarylamine with (di)benzothiophene/(di) benzofuran

US20070278938, US20080106190 US20110163302 Indolocarbazoles

Synth. Met. 111, 421 (2000) Isoindole compounds

Chem. Mater. 15, 3148 (2003) Metal carbene complexes

US20080018221 Phosphorescent OLED host materials Red hosts Arylcarbazoles

Appl. Phys. Lett. 78, 1622 (2001) Metal 8-hydroxyquinolates (e.g., Alq₃, BAlq)

Nature 395, 151 (1998)

US20060202194

WO2005014551

WO2006072002 Metal phenoxybenzothiazole compounds

Appl. Phys. Lett. 90, 123509 (2007) Conjugated oligomers and polymers (e.g., polyfluorene)

Org. Electron. 1, 15 (2000) Aromatic fused rings

WO2009066779, WO2009066778, WO2009063833, US20090045731, US20090045730, WO2009008311, US20090008605, US20090009065 Zinc complexes

WO2010056066 Chrysene based compounds

WO2011086863 Green hosts Arylcarbazoles

Appl. Phys. Lett. 78, 1622 (2001)

US20030175553

WO2001039234 Aryltriphenylene compounds

US20060280965

US20060280965

WO2009021126 Poly-fused heteroaryl compounds

US20090309488 US20090302743 US20100012931 Donor acceptor type molecules

WO2008056746

WO2010107244 Aza-carbazole/DBT/DBF

JP2008074939

US20100187984 Polymers (e.g., PVK)

Appl. Phys. Lett. 77, 2280 (2000) Spirofluorene compounds

WO2004093207 Metal phenoxybenzooxazole compounds

WO2005089025

WO2006132173

JP200511610 Spirofluorene-carbazole compounds

JP2007254297

JP2007254297 Indolocabazoles

WO2007063796

WO2007063754 5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole)

J. Appl. Phys. 90, 5048 (2001)

WO2004107822 Tetraphenylene complexes

US20050112407 Metal phenoxypyridine compounds

WO2005030900 Metal coordination complexes (e.g., Zn, Al with N{circumflex over ( )}N ligands)

US20040137268, US20040137267 Blue hosts Arylcarbazoles

Appl. Phys. Lett, 82, 2422 (2003)

US20070190359 Dibenzothiophene/ Dibenzofuran-carbazole compounds

WO2006114966, US20090167162

US20090167162

WO2009086028

US20090030202, US20090017330

US20100084966 Silicon aryl compounds

US20050238919

WO2009003898 Silicon/Germanium aryl compounds

EP2034538A Aryl benzoyl ester

WO2006100298 Carbazole linked by non- conjugated groups

US20040115476 Aza-carbazoles

US20060121308 High triplet metal organometallic complex

U.S. Pat. No. 7,154,114 Phosphorescent dopants Red dopants Heavy metal porphyrins (e.g., PtOEP)

Nature 395, 151 (1998) Iridium(III) organometallic complexes

Appl. Phys. Lett. 78, 1622 (2001)

US2006835469

US2006835469

US20060202194

US20060202194

US20070087321

US20080261076 US20100090591

US20070087321

Adv. Mater. 19, 739 (2007)

WO2009100991

WO2008101842

U.S. Pat. No. 7,232,618 Platinum(II) organometallic complexes

WO2003040257

US20070103060 Osminum(III) complexes

Chem. Mater. 17, 3532 (2005) Ruthenium(II) complexes

Adv. Mater. 17, 1059 (2005) Rhenium (I), (II), and (III) complexes

US20050244673 Green dopants Iridium(III) organometallic complexes

Inorg. Chem. 40, 1704 (2001)

US20020034656

U.S. Pat. No. 7,332,232

US20090108737

WO2010028151

EP1841834B

US20060127696

US20090039776

U.S. Pat. No. 6,921,915

US20100244004

U.S. Pat. No. 6,687,266

Chem. Mater. 16, 2480 (2004)

US20070190359

US 20060008670 JP2007123392

WO2010086089, WO2011044988

Adv. Mater. 16, 2003 (2004)

Angew. Chem. Int. Ed. 2006, 45, 7800

WO2009050290

US20090165846

US20080015355

US20010015432

US20100295032 Monomer for polymeric metal organometallic compounds

U.S. Pat. No. 7,250,226, U.S. Pat. No. 7,396,598 Pt(II) organometallic complexes, including polydentated ligands

Appl. Phys. Lett. 86, 153505 (2005)

Appl. Phys. Lett. 86, 153505 (2005)

Chem. Lett. 34, 592 (2005)

WO2002015645

US20060263635

US20060182992 US20070103060 Cu complexes

WO2009000673

US20070111026 Gold complexes

Chem. Commun. 2906 (2005) Rhenium(III) complexes

Inorg. Chem. 42, 1248 (2003) Osmium(II) complexes

U.S. Pat. No. 7,279,704 Deuterated organometallic complexes

US20030138657 Organometallic complexes with two or more metal centers

US20030152802

U.S. Pat. No. 7,090,928 Blue dopants Iridium(III) organometallic complexes

WO2002002714

WO2006009024

US20060251923 US20110057559 US20110204333

U.S. Pat. No. 7,393,599, WO2006056418, US20050260441, WO2005019373

U.S. Pat. No. 7,534,505

WO2011051404

U.S. Pat. No. 7,445,855

US20070190359, US20080297033 US20100148663

U.S. Pat. No. 7,338,722

US20020134984

Agnew. Chem. Int. Ed. 47, 1 (2008)

Chem. Mater. 18, 5119 (2006)

Inorg. Chem. 46, 4308 (2007)

WO2005123873

WO2005123873

WO2007004380

WO2006082742 Osmium(II) complexes

U.S. Pat. No. 7,279,704

Organometallics 23, 3745 (2004) Gold complexes

Appl. Phys. Lett. 74, 1361 (1999) Patinum(II) complexes

WO2006098120, WO2006103874 Pt tetradentate complexes with at least one metal- carbene bond

U.S. Pat. No. 7,655,323 Exciton/hole blocking layer materials Bathocuprine compounds (e.g., BCP, BPhen)

Appl. Phys. Lett. 75, 4 (1999)

Appl. Phys. Lett. 79, 449 (2001) Metal 8-hydroxyquinolates (e.g., BAlq)

Appl. Phys. Lett. 81, 162 (2002) 5-member ring electron deficient heterocycles such as triazole, oxadiazole, imidazole, benzoimidazole

Appl. Phys. Lett. 81, 162 (2002) Triphenylene compounds

US20050025993 Fluorinated aromatic compounds

Appl. Phys. Lett. 79, 156 (2001) Phenothiazine-S-oxide

WO2008132085 Silylated five-membered nitrogen, oxygen, sulfur or phosphorus dibenzoheterocycles

WO2010079051 Aza-carbazoles

US20060121308 Electron transporting materials Anthracene- benzoimidazole compounds

WO2003060956

US20090179554 Aza triphenylene derivatives

US20090115316 Anthracene-benzothiazole compounds

Appl. Phys. Lett. 89, 063504 (2006) Metal 8-hydroxy- quinolates (e.g., Alq₃, Zrq₄)

Appl. Phys. Lett. 51, 913 (1987) U.S. Pat. No. 7,230,107 Metal hydroxybenoquinolates

Chem. Lett. 5, 905 (1993) Bathocuprine compounds such as BCP, BPhen, etc

Appl. Phys. Lett. 91, 263503 (2007)

Appl. Phys. Lett. 79, 449 (2001) 5-member ring electron deficient heterocycles (e.g.,triazole, oxadiazole, imidazole, benzoimidazole)

Appl. Phys. Lett. 74, 865 (1999)

Appl. Phys. Lett. 55, 1489 (1989)

Jpn. J. Apply. Phys. 32, L917 (1993) Silole compounds

Org. Electron. 4, 113 (2003) Arylborane compounds

J. Am. Chem. Soc. 120, 9714 (1998) Fluorinated aromatic compounds

J. Am Chem. Soc. 122, 1832 (2000) Fullerene (e.g., C60)

US20090101870 Triazine complexes

US20040036077 Zn (N{circumflex over ( )}N) complexes

U.S. Pat. No. 6,528,187

EXPERIMENTAL

Chemical abbreviations used throughout this document are as follows: dba is dibenzylideneacetone, EtOAc is ethyl acetate, PPh₃ is triphenylphosphine, dppf is 1,1′-bis(diphenylphosphino)ferrocene, DCM is dichloromethane, SPhos is dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-3-yl)phosphine, THF is tetrahydrofuran.

Synthesis:

Synthesis of Compound A

Step 1

A mixture of 4-iododibenzo[b,d]furan (18.4 g, 62.6 mmol), 1H-imidazole (5.11 g, 75 mmol), CuI (0.596 g, 3.13 mmol), Cs₂CO₃ (42.8 g, 131 mmol), cyclohexane-1,2-diamine (1.43 g, 12.51 mmol) in DMF (200 mL) was heated at 150° C. under nitrogen for 20 hours. After cooling to room temperature, it was quenched with water and extracted with ethyl acetate. The combined extracts were washed with brine and filtered through a short plug of silica gel. Upon evaporation off the solvent, the crude product was dissolved in ethyl acetate and precipitated in hexane to yield 1-dibenzo[b,d]furan-4-yl)-1H-imidazole (12.2 g, 83%) as a white solid.

Step 2

A solution of 1-dibenzo[b,d]furan-4-yl)-1H-imidazole (10 g, 42.7 mmol) and iodomethane (30.3 g, 213 mmol) in ethyl acetate (100 mLl) was stirred at room temperature for 24 h. The precipitation was isolated by filtration to yield 1-(dibenzo[b,d]furan-4-yl)-3-methyl-1H-imidazol-3-ium iodide (15.3 g, 93%) as a white solid.

Step 3

A mixture of 1-(dibenzo[b,d]furan-4-yl)-3-methyl-1H-imidazol-3-ium iodide (2.5 g, 6.65 mmol) and Ag₂O (0.770 g, 3.32 mmol) in acetonitrile (150 mL) was stirred under nitrogen overnight. After evaporation off the solvent, the iridium phenylimidazole complex (2.58 g, 2.215 mmol) and THF (150 mL) was added. The resultant reaction mixture was refluxed under nitrogen overnight. After cooling to room temperature, it was filtered through a short plug of Celite® and the solid was washed with DCM. The combined filtrates were evaporated and the residue was purified by column chromatography on triethylamine-treated silica gel with hexane/DCM (9/1 to 3/1, v/v) as eluent to yield the mer form of Compound A (1.9 g, 72%) as a green yellow solid.

Step 4

A solution of mer form (1.9 g, 1.584 mmol) in anhydrous DMSO (100 mL) was irradiated with UV light (365 nm) under nitrogen for 3.5 h. Upon evaporation off the solvent, the residue was purified by column chromatography on triethylamine-treated silica gel with hexane/DCM (3/1, v/v) as eluent, followed by boiling in toluene to yield Compound A (1.2 g, 62%) as a green yellow solid.

Synthesis of Compound 17

Step 1

1-Dibenzo[b,d]furan-4-yl)-1H-imidazole (4.5 g, 19.21 mmol) was dissolved in MeCN (100 mL) in a 250 mL flask. To the mixture, 2-iodopropane (16.33 g, 96 mmol) was added. The reaction mixture was refluxed for 72 hours under N₂. After removal of solvent, the residue was dissolved in a minimum amount ethyl acetate and precipitated in ether to obtain the product (6.7 g, 86%) as a brown solid after decanting solvent and drying under vacuum.

Step 2

The iodide salt (2.3 g, 5.12 mmol) from step 1, Ag₂O (0.593 g, 2.56 mmol) and dry acetonitrile (200 mL) were charged in a 250 mL flask. The mixture was stirred overnight at room temperature and the solvent was evaporated. To the residue, iridium dimer (2.85 g, 1.707 mmol) and THF (200 mL) were added. The reaction mixture was refluxed overnight. The mixture was cooled down and run through a Celite® bed with THF. Crude mer isomer (2.85 g, 78%) was obtained after evaporation of THF and washing with methanol.

Step 3

The mer isomer (2.4 g, 2.232 mmol) from Step 2 was dissolved in DMSO (400 mL) with heating in a photoreaction flask. The mixture was cooled down to room temperature. The solution was pumped and purged with N₂ a few times, and then irradiated with a UV lamp (365 nm) under N₂ for 13 hours until HPLC showed the mer isomer was converted to fac isomer. The product was purified by silica gel column chromatography with DCM in hexane as eluent to obtain pure fac complex (1.6 g, 66.7%). Both NMR and LC-MS confirmed the desired product.

Synthesis of Compound 27

Step 1

A solution of 1-(dibenzo[b,d]furan-4-yl)-3-isopropyl-1H-imidazol-3-ium iodide (1.536 g, 3.80 mmol) and Ag₂O (0.514 g, 2.217 mmol) in acetonitrile (50 mL) was stirred under nitrogen overnight. The solvent was evaporated and the iridium complex dimmer (2.5 g, 1.267 mmol) was added together with THF (50 mL). The resultant mixture was refluxed under nitrogen overnight. After cooling to room temperature, it was filtered through a short plug of Celite® and the solid was washed with DCM. The combined filtrates were evaporated and the residue was purified by column chromatography on triethylamine-treated silica gel with hexane/DCM (9/1, v/v) as eluent to yield the mer isomer (2.3 g, 74%) as a green yellow solid.

Step 2

A solution of mer form (2.3 g, 1.874 mmol) in DMSO (100 mL) was irradiated with UV light under nitrogen for 4 hours. Upon evaporation of the solvent, the residue was purified by column chromatography on triethylamine-treated silica gel with hexane/DCM (9/1 to 4/1, v/v) as eluent to yield Compound 27 (1.6 g, 70%) as a green yellow solid.

Synthesis of Compound 62

Step 1

1-Dibenzo[b,d]furan-4-yl)-1H-imidazole (2.0 g, 8.54 mmol) was dissolved in ethyl acetate (100 mL) in a 250 mL flask. To the mixture was added MeI-d3 (6.2 g, 43 mmol). The reaction mixture was stirred at room temperature for 72 hours under N₂. After filtration, the product (3.1 g, 96%) was obtained as a white solid was obtained.

Step 2

The salt from step 1 (2.0 g, 5.27 mmol), Ag₂O (0.617 g, 2.64 mmol) and dry acetonitrile (200 mL) were charged in a 250 mL flask. The mixture was stirred at room temperature overnight, and the solvent was evaporated. To the residue were added iridium dimer (2.93 g, 1.758 mmol) and THF (200 mL). The reaction mixture was then refluxed overnight. The mixture was cooled down and run through a Celite® bed with THF to produce 2.8 g (76% yield) of crude mer isomer after evaporating the THF and washing with methanol.

Step 3

The mer isomer (2.4 g, 2.285 mmol) was dissolved in DMSO (400 mL) with heating in a photoreaction flask. The mixture was cooled down to room temperature. The solution was pumped and purged with N₂ for few times, then irradiated with UV lamp (365 nm) under N₂ for 8 hours until HPLC shown the mer isomer was converted to the fac isomer. The product was purified by silica gel column with DCM in hexane as eluent. Pure fac complex, Compound 62 (1.6 g, 66.7%), was obtained after column chromatography. Both NMR and LC-MS confirmed the desired product.

It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting. 

The invention claimed is:
 1. A first device comprising an organic light emitting device, comprising: an anode; a cathode; a first layer disposed between the anode and the cathode; and a second layer disposed between the first layer and the cathode; wherein the first layer is an emissive layer comprising an emissive dopant, a host, and a co-host; wherein the second layer is a non-emissive layer comprising a first metal carbene complex; wherein the second layer is a hole blocking layer; wherein the host is a second metal carbene complex; wherein the co-host is a non-emissive dopant, and the non-emissive dopant is a fourth metal carbene complex; and wherein the emissive dopant is a fifth metal-carbene complex, wherein the host and the co-host are different and have a structure of Formula

wherein M is a metal having an atomic number greater than 40; wherein A₁, A₂ are each independently selected from the group consisting of C or N; wherein Ring A and Ring B are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; wherein R_(A) and R_(B) represent mono, di, tri, or tetra substitutions or no substitution; wherein X is selected from the group consisting of NR_(C), PR_(C), O, and S; wherein each of R_(A), R_(B), and R_(C) are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined together to form a ring, which may be further substituted; wherein the ligand L is another ligand coordinated to the metal M; wherein m is a value from 1 to the maximum number of ligands that may be attached to the metal; wherein m+n is the maximum number of ligands that may be attached to metal M; wherein, in the host, R^(B) is not a fused heterocyclic ring with N as the heteroatom, ring A is 6-membered aryl or heteroaryl ring, A₂ is C, and R_(A) is an electron withdrawing group with a Hammett constant larger than 0 when ring A is 6-membered aryl ring; and wherein, in the co-host, R_(B) is a fused heterocyclic ring with N as the heteroatom, where the fused heterocyclic ring is optionally further substituted.
 2. The first device of claim 1, wherein the device further comprises a third layer disposed between the anode and the first layer; and wherein the third layer that is a non-emissive layer comprises a third metal carbene complex, and wherein the first metal carbene complex and the third metal carbene complex are different.
 3. The first device of claim 2, wherein the third layer is selected from the group consisting of an electron blocking layer, an exciton blocking layer, and a hole transporting layer.
 4. The first device of claim 2, wherein the first, second, and third layers contain only metal carbene complexes.
 5. The first device of claim 1, wherein the first metal carbene complex and the fourth metal carbene complex are the same.
 6. The first device of claim 1, wherein the first metal carbene complex and the fifth metal carbene complex are different.
 7. The first device of claim 1, wherein the first metal carbene complex has the formula:

wherein M is a metal having an atomic number greater than 40; wherein A₁, A₂ are each independently selected from the group consisting of C or N; wherein A and B are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; wherein R_(A) and R_(B) represent mono, di, tri, or tetra substitutions or no substitution; wherein X is selected from the group consisting of NR_(C), PR_(C), O, and S; wherein each of R_(A), R_(B), and R_(C) are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined together to form a ring, which may be further substituted; wherein the ligand L is another ligand coordinated to the metal M; wherein m is a value from 1 to the maximum number of ligands that may be attached to the metal; and wherein m+n is the maximum number of ligands that may be attached to metal M.
 8. The first device of claim 7, wherein the metal is Ir or Pt.
 9. The first device of claim 7, wherein X is NR_(C).
 10. The first device of claim 7, wherein R_(B) is a fused heterocyclic ring; wherein the heteroatom in the fused heterocyclic ring is N; and wherein the fused heterocyclic ring is optionally further substituted.
 11. The first device of claim 7, wherein R_(A) is an electron withdrawing group with Hammett constant larger than
 0. 12. The first device of claim 1, wherein the first device is a consumer product selected from the group consisting of flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a wall, theater or stadium screens, and signs.
 13. The first device of claim 1, wherein the emissive dopant is a heteroleptic iridium complex having the formula:

wherein R₂, R_(x), R_(a), and R_(b), represent mono, di, tri, tetra substitutions or no substitution; wherein R₁ is an alkyl or cycloalkyl with a molecular weight higher than 15.5 g/mol; wherein X is selected from the group consisting of CRR′, SiRR′, C═O, N—R, B—R, O, S, SO, SO₂, and Se; wherein R, R′, R₂, R_(x), R_(a), R_(b), and R_(c) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined to form a ring, which may be further substituted; and wherein n is 1 or
 2. 14. The first device of claim 1, wherein the emissive dopant is a heteroleptic iridium complex having the formula:

wherein R₂, R_(x), R_(a), and R_(b), represent mono, di, tri, tetra substitutions or no substitution; wherein R₁ is an alkyl or cycloalkyl with a molecular weight higher than 15.5 g/mol; wherein X is selected from the group consisting of CRR′, SiRR′, C═O, N—R, B—R, O, S, SO, SO₂, and Se; wherein R, R′, R₂, R_(x), R_(a), R_(b), and R_(c) are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined to form a ring, which may be further substituted; and wherein n is 1 or
 2. 15. The first device of claim 14, wherein the first metal carbene complex and the fourth metal carbene complex are homoleptic.
 16. The first device of claim 15, wherein the first metal carbene complex and the fourth metal carbene complex are the same.
 17. The first device of claim 16, wherein the first metal carbene complex has the formula:

wherein M is a metal having an atomic number greater than 40; wherein R_(A) and R_(B) represent mono, di, tri, or tetra substitutions or no substitution; wherein each of R_(A), R_(B), and R_(C) are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined together to form a ring, which may be further substituted; wherein m is a maximum number of ligands that may be attached to the metal.
 18. The first device of claim 1, wherein the host is selected from the group consisting of:


19. The first device of claim 18 wherein the co-host is selected from the group consisting of: 